Co-reporter:Jian-Gang Xu, Cai Sun, Ming-Jian Zhang, Bin-Wen Liu, Xiao-Zhen Li, Jian Lu, Shuai-Hua Wang, Fa-Kun Zheng, and Guo-Cong Guo
Chemistry of Materials November 28, 2017 Volume 29(Issue 22) pp:9725-9725
Publication Date(Web):November 3, 2017
DOI:10.1021/acs.chemmater.7b03453
Advancement in explosive systems toward miniaturization and enhanced safety has prompted the development of primary explosives with powerful detonation performance and relatively low sensitivities. Energetic coordination polymers (ECPs) as a new type of energetic materials have attracted wide attention. However, regulating the energetic characters of ECPs and establishing the relationship between structure and energetic property remains great challenges. In this study, two isomorphic 2D π-stacked solvent-free coordination polymers, [M(N3)2(atrz)]n (M = Co 1, Cd 2; atrz = 4,4′-azo-1,2,4-triazole), were hydrothermally prepared and structurally characterized by X-ray diffraction. The two compounds exhibit reliable stabilities, remarkable positive enthalpies of formation, and prominent heats of detonation. The enthalpy of formation of 1 is 4.21 kJ·g–1, which is higher than those of all hitherto known primary explosives. Repulsive steric clashes between the sensitive azide ions in 1 and 2 influence the mechanical sensitivities deduced from the calculated noncovalent interaction domains. The two energetic π-stacked ECPs 1 and 2 can serve as candidates for primary explosives with an approved level of safety.
Co-reporter:Jian-Gang Xu, Shuai-Hua Wang, Ming-Jian Zhang, Cai Sun, Yu Xiao, Rong Li, Fa-Kun Zheng, Guo-Cong Guo, and Jin-Shun Huang
ACS Omega January 2017? Volume 2(Issue 1) pp:346-346
Publication Date(Web):January 31, 2017
DOI:10.1021/acsomega.6b00431
For designing energetic materials (EMs), the most challenging issue is to achieve a balance between energetic performance and reliable stability. In this work, we employed an efficient and convenient method to synthesize a new class of EMs: nitrogen-rich tetranuclear metal complexes [M(Hdtim)(H2O)2]4 (M = Zn 1, Mn 2; H3dtim = 1H-imidazol-4,5-tetrazole) with the N content of >46%. The structural analyses illustrate that isomorphous compounds 1 and 2 feature isolated hollow ellipsoid tetranuclear units, which are linked by both π–π interactions and hydrogen-bonding interactions to give a 3D supramolecular architecture. Compounds 1 and 2 exhibit prominent energetic characteristics: excellent detonation performances and reliable thermal, impact, and friction stabilities. Being nitrogen-rich tetrazolate compounds, the enthalpies of combustion of 1 (−11.570 kJ g–1) and 2 (−12.186 kJ g–1) are higher than those of classical EMs, RDX and HMX, and they possess high positive heats of formation. Sensitivity tests demonstrate that 1 and 2 are insensitive to external mechanical action. Excellent energetic performances and low sensitivities promote 1 and 2 to serve as a new class of promising EMs with a desirable level of safety.Topics: Coordination compounds; Enthalpy; Enthalpy; Materials processing; Mechanical properties; Thermal properties;
Co-reporter:Li-Zhen Cai;Zhang-Jing Zhang;Pei-Yu Guo;Ai-Ping Jin;Xiao-Ming Jiang;Ming-Sheng Wang
Inorganic Chemistry February 6, 2017 Volume 56(Issue 3) pp:1036-1040
Publication Date(Web):January 10, 2017
DOI:10.1021/acs.inorgchem.6b02671
Vapor-responsive magnetic materials are highly promising for applications as chemical switches or sensors. Compared with porous materials, nonporous species benefit in overcoming the intrinsic conflict between magnetic exchange and porosity but usually suffer from the powdering of single crystals, which hinders the understanding of the structural nature of vapor response and magnetic switch. Single-crystal-to-single-crystal (SCSC) transformation of nonporous compounds through the desorption/absorption of gaseous HCl is unprecedented. Reported here is a discrete nonporous copper(II) complex, (H3O)[K(15-crown-5)2][CuCl4], that exhibits reversible SCSC transformation and magnetic change by the chemisorption/desorption of HCl and H2O. Significant changes in the coordination number (4 ↔ 3), space group (P1̅ ↔ P21/c), color (green ↔ red), and magnetic behavior (antiferromagnetic ↔ paramagnetic) were found during the SCSC transformation.
Co-reporter:Yu-Hang Fan, Xiao-Ming Jiang, Bin-Wen Liu, Shu-Fang Li, Wei-Huan Guo, Hui-Yi Zeng, Guo-Cong GuoJin-Shun Huang
Inorganic Chemistry 2017 Volume 56(Issue 1) pp:114-124
Publication Date(Web):December 16, 2016
DOI:10.1021/acs.inorgchem.6b01016
Two new phases in the Ag–Cd–P–S system containing two second-order Jahn–Teller (SOJT) distorted d10 cations (Cd2+ and Ag+), namely, Ag2Cd(P2S6) (1) and AgCd3(PS4)S2 (2), are obtained via medium-temperature solid-state synthesis. Compound 1 exhibits a two-dimensional layered structure and undergoes a first-order structural phase transition at approximately 280 °C. This outcome can be ascribed to the significant mismatch in the expansion coefficients between Cd–S (Ag–S) and P–P (P–S) bonds evaluated through bond valence theory. The three-dimensional non-centrosymmetric (NCS) framework of 2 is constructed by two types of tetrahedral layers consisting of corner-shared CdS4, AgS4, and PS4 tetrahedra. Compound 2 exhibits second harmonic generation (SHG) intensity of 0.45 times that of commercial AgGaS2 (AGS) at a laser irradiation of 1.85 μm and an optical band gap of 2.56 eV, and no intrinsic vibrational absorption of chemical bonds is observed in the range of 2.5–18.2 μm. Both phase transition in 1 and SHG properties in 2 are closely related to the SOJT distorted d10 cations and diverse phosphorus–sulfur polyanions (PaSb)n−, which together can easily result in NCS distorted structures and interesting properties.
Co-reporter:Ning-Ning Zhang;Cai Sun;Xiao-Ming Jiang;Xiu-Shuang Xing;Yong Yan;Li-Zhen Cai;Ming-Sheng Wang
Chemical Communications 2017 vol. 53(Issue 66) pp:9269-9272
Publication Date(Web):2017/08/15
DOI:10.1039/C7CC05446G
White light emission from single-component small organic triazole molecules in the solid state was observed for the first time. This unusual intrinsic broadband emission, stemming from the supramolecular aggregate instead of the excimer, can be tuned by controlling the degree of electron delocalization and intensities of intermolecular interactions.
Co-reporter:Xiu-Shuang Xing;Rong-Jian Sa;Pei-Xin Li;Ning-Ning Zhang;Zhong-Yuan Zhou;Bin-Wen Liu;Jie Liu;Ming-Sheng Wang
Chemical Science (2010-Present) 2017 vol. 8(Issue 11) pp:7751-7757
Publication Date(Web):2017/10/23
DOI:10.1039/C7SC01228D
Nonlinear optical (NLO) switchable materials are important for photonic and optoelectronic technologies. One important issue for NLO photoswitching, the most studied physical switching approach, is how to improve the switching contrast of second harmonic generation (SHG) in crystals, because the known values are generally below 3 times. Thermoswitching, as another approach, has shown impressive high SHG-switching contrasts (4–∞ times), but the fast decay of thermally induced states demands constant heat sources to maintain specific SHG intensities. We have synthesized a photochromic and thermochromic bistable acentric compound, β-[(MQ)ZnCl3] (MQ+ = N-methyl-4,4′-bipyridinium), which represents the first crystalline compound with both photo- and heat-induced SHG-switching behavior and the first example of a thermoswitchable NLO crystal that can maintain its expected second-order NLO intensity without any heat source. The SHG-switching contrast can reach about 8 times after laser irradiation or 2 times after thermal annealing. The former value is the highest recorded for photoswitchable NLO crystals. This work also indicates that higher SHG-switching contrasts may be obtained through increasing electron-transfer efficiency, variation of permanent dipole moment, and self-absorption.
Co-reporter:Guan-E Wang;Ming-Shui Yao;Min-Lan Cai;Jing-Wei Xiu;Yan-Zhou Li;Gang Xu
Journal of Materials Chemistry A 2017 vol. 5(Issue 35) pp:18409-18413
Publication Date(Web):2017/09/12
DOI:10.1039/C7TA05805E
Crystalline materials possessing both porous and conductive properties would create a great opportunity for novel electrical applications in fuel cells, batteries and sensors. However, these kinds of materials are rarely reported. Here, we report a new type of conducting porous crystalline material constructed by long distance Coulomb interactions among inorganic and organic components. The compound in this work shows a microporous structure, typical semiconductive properties, selective adsorption and an interesting electrical response to methanol and ethanol.
Co-reporter:Jie Liu;Pei-Xin Li;Hui-Yi Zeng
RSC Advances (2011-Present) 2017 vol. 7(Issue 55) pp:34901-34906
Publication Date(Web):2017/07/07
DOI:10.1039/C7RA05352E
Recent research has demonstrated the effective synthesis of photochromic coordination compounds via the assembly of nonphotochromic ligands (electronic donors and acceptors) and a metal center (joint points). To enrich this system, the metal center could be expanded to binuclear or multinuclear, but related studies are rare. Two new photochromic coordination compounds with different metal joint dots were obtained using expanded metal centers. In this work, [Zn2(Bpy)1.5(CTA)4·2H2O] (1, CTA = crotonic acid, Bpy = 4,4′-bipyridine) and [Zn2(Bpy)(CTA)4] (2) were synthesized under different pH conditions. Compound 1 features a 1-D chain structure with 4,4′-bipyridine coordinating to mono zinc ions and binuclear Zn units simultaneously. Compound 2 also features a 1-D chain structure, where only the binuclear Zn is bridged by the 4,4′-bipyridine. This work will help to obtain new and promising photochromic compounds with different multinuclear metal centers and high performance.
Co-reporter: Dr. Cong Bin Fan;Le Le Gong;Dr. Ling Huang; Dr. Feng Luo; Dr. Rajamani Krishna;Xian Feng Yi; Dr. An Min Zheng;Le Zhang;Shou Zhi Pu;Xue Feng Feng;Ming Biao Luo; Dr. Guo Cong Guo
Angewandte Chemie International Edition 2017 Volume 56(Issue 27) pp:7900-7906
Publication Date(Web):2017/06/26
DOI:10.1002/anie.201702484
AbstractA dual temperature- and light-responsive C2H2/C2H4 separation switch in a diarylethene metal–organic framework (MOF) is presented. At 195 K and 100 kPa this MOF shows ultrahigh C2H2/C2H4 selectivity of 47.1, which is almost 21.4 times larger than the corresponding value of 2.2 at 293 K and 100 kPa, or 15.7 times larger than the value of 3.0 for the material under UV at 195 K and 100 kPa. The origin of this unique control in C2H2/C2H4 selectivity, as unveiled by density functional calculations, is due to a guest discriminatory gate-opening effect from the diarylethene unit.
Co-reporter: Dr. Cong Bin Fan;Le Le Gong;Dr. Ling Huang; Dr. Feng Luo; Dr. Rajamani Krishna;Xian Feng Yi; Dr. An Min Zheng;Le Zhang;Shou Zhi Pu;Xue Feng Feng;Ming Biao Luo; Dr. Guo Cong Guo
Angewandte Chemie 2017 Volume 129(Issue 27) pp:8008-8014
Publication Date(Web):2017/06/26
DOI:10.1002/ange.201702484
AbstractA dual temperature- and light-responsive C2H2/C2H4 separation switch in a diarylethene metal–organic framework (MOF) is presented. At 195 K and 100 kPa this MOF shows ultrahigh C2H2/C2H4 selectivity of 47.1, which is almost 21.4 times larger than the corresponding value of 2.2 at 293 K and 100 kPa, or 15.7 times larger than the value of 3.0 for the material under UV at 195 K and 100 kPa. The origin of this unique control in C2H2/C2H4 selectivity, as unveiled by density functional calculations, is due to a guest discriminatory gate-opening effect from the diarylethene unit.
Co-reporter: Dr. Cong Bin Fan;Le Le Gong;Dr. Ling Huang; Dr. Feng Luo; Dr. Rajamani Krishna;Xian Feng Yi; Dr. An Min Zheng;Le Zhang;Shou Zhi Pu;Xue Feng Feng;Ming Biao Luo; Dr. Guo Cong Guo
Angewandte Chemie 2017 Volume 129(Issue 27) pp:8127-8127
Publication Date(Web):2017/06/26
DOI:10.1002/ange.201704765
Selektive Adsorption und Trennung durch photochrome Metall-organische Gerüste (MOFs) lässt sich bisher nur selten allein durch externe Reize einstellen. In der Zuschrift auf S. 8008 ff. setzen F. Luo, G.-C. Guo et al. eine photochrome Diarylethen-Einheit zur lichtresponsiven Steuerung von Selektivität und Trennverhalten ein. Dadurch erhalten sie eine hoch selektive Adsorption, zum Beispiel im System C2H2/C2H4.
Co-reporter:Zhiqiao Wang;Zhongning Xu;Siyan Peng;Zhangfeng Zhou;Pengbin Pan;Lin Lin;Yeyan Qin;Guocong Guo;Yuangen Yao
Chinese Journal of Chemistry 2017 Volume 35(Issue 6) pp:759-768
Publication Date(Web):2017/06/01
DOI:10.1002/cjoc.201600746
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has achieved the industrialization of the first generation catalysts for coal to ethylene glycol for the first time in 2009. However, there are still lots of aspects to be improved, such as high noble metal loading and toxic Cr in catalyst of ester hydrogenation. To improve the catalysts, we have done systematic deep research about the nanostructures of catalysts, and revealed facet effect, size effect, synergistic effect, support effect, and so on. A series of catalysts preparation technologies have been developed to achieve the efficient utilization of noble metals. The Pd loadings of dehydrogenation catalyst and CO oxidative coupling catalyst have been dropped from 2.5% to 0.9% and 2.0% to 0.13%, respectively, while the catalytic performances are enhanced greatly. The toxic Cu-Cr in ester hydrogenation catalyst has been upgraded to green Cu-Si. The new catalysts for coal to ethylene glycol with advancement have been successfully developed with independent intellectual property rights.
Co-reporter:Shu-Fang Li, Xiao-Ming Jiang, Bin-Wen Liu, Dong Yan, Chen-Sheng Lin, Hui-Yi Zeng, and Guo-Cong Guo
Chemistry of Materials 2017 Volume 29(Issue 4) pp:
Publication Date(Web):January 30, 2017
DOI:10.1021/acs.chemmater.6b05405
Developing excellent infrared nonlinear optical (NLO) materials is challenging because of the incompatibility between a large second harmonic generation (SHG) efficiency and a high laser-induced damage threshold (LIDT). Here, we report three NLO chalcogenides, namely, Na2In4SSe6 (1), NaGaIn2Se5 (2), and NaIn3Se5 (3), whose crystal structures consist of supertetrahedral, superpentahedral, and superoctahedral chalcogenide clusters. Importantly, they exhibit SHG responses 7.0-, 2.1-, and 0.3-fold larger than and LIDTs 5.8-, 6.4-, and 10.7-fold higher than those of AgGaS2, respectively, almost achieving balance between large SHG efficiencies and high LIDTs. Theoretical calculations and structural analysis reveal that the enhanced SHG responses can be attributed to the superpolyhedral chalcogenide clusters. The high LIDTs can be ascribed to their small thermal expansion anisotropy. These findings may provide useful insights into the development of infrared NLO materials with superpolyhedron-built structures.
Co-reporter:Yu-Hang Fan, Hui-Yi Zeng, Xiao-Ming Jiang, Ming-Jian Zhang, Bin-Wen Liu, Guo-Cong GuoJin-Shun Huang
Inorganic Chemistry 2017 Volume 56(Issue 2) pp:
Publication Date(Web):January 5, 2017
DOI:10.1021/acs.inorgchem.6b02667
Quaternary metal thiophosphates containing second-order Jahn–Teller distorted d10 Ag+ and lone-pair cations, Ag3Bi(PS4)2 (1), Ag7Sn(PS4)3 (2), and Ag7Pb(PS4)3 (3), were obtained by solid-state synthesis. The structural frameworks of 2 and 3 feature an infinite 1-D interchiral double helix ∞1(Ag3P2S11), which is rare in inorganic compounds. Compound 3 undergoes a significant first-order structural phase transition from monoclinic to hexagonal at ∼204 °C. This can be ascribed to the significant mismatch in the expansion coefficients between Pb–S (Ag–S) and P–S bonds evaluated by bond valence theory. The three compounds are Ag+ ionic conductors, and Ag+ ion migration pathways are proposed by calculating maps of low bond valence mismatch. Moreover, the optical properties of the three compounds were studied, and electronic structure calculations were performed. The combination of second-order Jahn–Teller distorted d10 cation and lone-pair cation provides a new strategy to explore new metal thiophosphates with interesting structures and promising properties.
Co-reporter:Cai Sun;Ming-Sheng Wang;Xian Zhang;Ning-Ning Zhang;Lin-Rong Cai
CrystEngComm (1999-Present) 2017 vol. 19(Issue 31) pp:4476-4479
Publication Date(Web):2017/08/07
DOI:10.1039/C7CE00919D
Changing N-substituents to modify energy gaps is important for the diverse applications (photochromism, photocatalysis, etc.) of viologen-based compounds. In situ N-substitution using alcohols under solvothermal and acidic conditions is an effective and common synthetic method for viologen-templated metal halides. In this work, we found that replacing alcohols with alkenes could reduce the reaction temperature dramatically to room temperature. A new cis/trans-viologen-templated bromoplumbate with a novel 1-D chain structure built by edge-sharing planar [Pb3Br9]3− oligomers was successfully obtained. This bromoplumbate hybrid has a narrower energy gap compared with bulk PbBr2, which has been well explained by linear optical response spectra calculations and PDOS analysis.
Co-reporter:Hong-Zi Tan;Zhi-Qiao Wang;Zhong-Ning Xu;Jing Sun;Zhe-Ning Chen;Qing-Song Chen;Yumin Chen
Catalysis Science & Technology (2011-Present) 2017 vol. 7(Issue 17) pp:3785-3790
Publication Date(Web):2017/08/29
DOI:10.1039/C7CY01305A
Palladium (Pd)-based catalysts have been widely used for carbonylation of methyl nitrite to dimethyl carbonate (DMC), but a high-performance chloride free catalyst combining both excellent carbon monoxide (CO) conversion and DMC selectivity has not been developed yet. In this work, a chloride free, Pd-based catalyst with good activity and selectivity (conversion of CO: 60.1%, selectivity to DMC: 99.9%) has been successfully fabricated. By thorough characterization and analysis, it is found that the good catalytic activity is positively correlated with the high oxidation states of the Pd species, which could be tuned by their ability to accept the backdonation electron of the ligands. The strong electron backdonation from Pd to π* antibonding orbitals of the ligand in the palladium acetylacetonate [Pd(acac)2] complex accelerates the step where Pdδ+ reoxidizes to Pd(II), resulting in the higher catalytic activity. In addition, a catalytic mechanism was proposed based on the results of X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared spectroscopy. This work not only explains the positive relationship between the catalytic activity and the oxidation state of the Pd species, but also provides a new way to enhance catalytic performance by utilizing the abilities of accepting the backdonation electron of the ligands.
Co-reporter: Dr. Cong Bin Fan;Le Le Gong;Dr. Ling Huang; Dr. Feng Luo; Dr. Rajamani Krishna;Xian Feng Yi; Dr. An Min Zheng;Le Zhang;Shou Zhi Pu;Xue Feng Feng;Ming Biao Luo; Dr. Guo Cong Guo
Angewandte Chemie International Edition 2017 Volume 56(Issue 27) pp:8015-8015
Publication Date(Web):2017/06/26
DOI:10.1002/anie.201704765
Adjusting adsorption selectivity and separation in photochromic metal–organic frameworks (MOFs) just by external stimuli is highly important but still rare. In their Communication on page 7900 ff., F. Luo, G.-C. Guo, and co-workers employ a photochromic diarylethene unit as a light-triggered selectivity and separation regulator, leading to ultrahigh adsorption selectivity, for example, for the mixture C2H2/C2H4.
Co-reporter:Bin-Wen Liu, Hui-Yi Zeng, Xiao-Ming Jiang, Guan-E Wang, Shu-Fang Li, Li Xu and Guo-Cong Guo
Chemical Science 2016 vol. 7(Issue 9) pp:6273-6277
Publication Date(Web):01 Jun 2016
DOI:10.1039/C6SC01907B
Mid-far infrared (IR) non-linear optical (NLO) materials are of great importance in military and civil fields. However, commercial IR-NLO crystals (such as AgGaS2, AgGaSe2 and ZnGeP2) do not currently satisfy the requirements of large second-harmonic generation (SHG) and high laser induced damage thresholds (LIDTs), which seriously limits their practical applications. Herein, we have developed a new series of salt-inclusion chalcogenides, [A3X][Ga3PS8] (A = K, Rb; X = Cl, Br), which are constructed from alternate stacking of adamantane-like [Ga3PS10]6− cluster layers and cationic [A3X]2+ salt layers. Importantly, they display both large SHG responses of several-fold and high LIDTs for dozens of times that of commercial AgGaS2, which exhibit the highest LIDTs among the reported IR-NLO materials with a larger SHG conversion efficiency than that of AgGaS2. These properties together with wide transparent region, type I phase-matching features and congruent-melting behaviors indicate they are promising IR-NLO materials.
Co-reporter:Xian Zhang, Ming-Sheng Wang, Cai Sun, Chen Yang, Pei-Xin Li and Guo-Cong Guo
Chemical Communications 2016 vol. 52(Issue 51) pp:7947-7949
Publication Date(Web):23 May 2016
DOI:10.1039/C6CC03354G
With the help of theoretical predictions, we have found, from the [donor–metal–acceptor] system, the first photochromic pyrazine-based compound that can undergo photoinduced charge separation and yield stable pyrazine radicals.
Co-reporter:Shu-Fang Li, Bin-Wen Liu, Ming-Jian Zhang, Yu-Hang Fan, Hui-Yi Zeng, and Guo-Cong Guo
Inorganic Chemistry 2016 Volume 55(Issue 4) pp:1480-1485
Publication Date(Web):February 4, 2016
DOI:10.1021/acs.inorgchem.5b02211
The first two new Na-containing sulfides Na2In2MS6 (M = Si (1), Ge (2)) in the Na2Q–B2Q3–CQ2 (B = Ga, In; C = Si, Ge, Sn; Q = S, Se) system were prepared for the first time through conventional high-temperature solid-state reaction. They are isostructural with space group Cc (No. 9) in monoclinic phases and feature three-dimensional frameworks built by the ∞1[In2MS6]2– (M = Si, Ge) chains through corner-sharing InS4 tetrahedra and MS4 (M = Si, Ge) tetrahedra, with Na+ cation located in the cavities. They display moderate second harmonic generation (SHG) conversion efficiencies compared with commercial AgGaS2, with phase-matching behavior at 1800 nm and laser-induced damage thresholds 6.9 and 4.0 times higher than that of AgGaS2, respectively. Therefore, the output SHG intensities of 1 and 2 will be ∼4.3 and 4.0 times larger than that of AgGaS2, when the intensity of incident laser increased to close the damage energy of 1 and 2, indicating their potential for high-power nonlinear optical application.
Co-reporter:Sheng-Ping Guo, Yang Chi, Bin-Wen Liu and Guo-Cong Guo
Dalton Transactions 2016 vol. 45(Issue 25) pp:10459-10465
Publication Date(Web):16 May 2016
DOI:10.1039/C6DT01602B
A novel pentanary selenide (K3I)[InB12(InSe4)3] was obtained via a high-temperature solid-state method. It crystallizes in the hexagonal space group P6322 which features an InSe4 tetrahedron consolidated B12 icosahedron and 1-D chain constructed by InSe6 octahedron and B12Se12 cluster alternatively connected along the c-axis. Second-order nonlinear optical property measurement shows that it is second harmonic generation-active. Theory calculation indicates that it is an indirect semiconductor with the energy gap of 1.15 eV.
Co-reporter:Rong Li, Shuai-Hua Wang, Zhi-Fa Liu, Xu-Xing Chen, Yu Xiao, Fa-Kun Zheng, and Guo-Cong Guo
Crystal Growth & Design 2016 Volume 16(Issue 7) pp:3969-3975
Publication Date(Web):May 17, 2016
DOI:10.1021/acs.cgd.6b00528
An azole-based metal–organic framework [Cd(tzphtpy)2]n·6.5nH2O, hydrothermally synthesized from the reaction mixture of a π-electron rich azole ligand 4-(tetrazol-5-yl)phenyl-2,2′:6′,2″-terpyridine (Htzphtpy) and CdBr2·4H2O, displays direct white-light emissions at a wide range of excitation wavelengths (286–386 nm) through modulating the relative intensity of complementary yellow and blue colors. Photoluminescence experiments and density of states and the calculations of time-dependent density functional theory demonstrate that the higher-energy blue emission is attributed to intraligand charge transfer, and the lower-energy yellow emission is related to interligand π–π interactions. The synergism of ligand-centered charge transfer and interligand π–π interactions is first found in white-light emitting azole-based metal–organic frameworks. Our work provides a new synthetic strategy for azole-based or other system white-light emitting materials.
Co-reporter:Pei-Xin Li, Ming-Sheng Wang, and Guo-Cong Guo
Crystal Growth & Design 2016 Volume 16(Issue 7) pp:3709-3715
Publication Date(Web):May 4, 2016
DOI:10.1021/acs.cgd.6b00195
The past years have evidenced the rapid development of photochromic coordination compounds; however, the impact of coordination on the photochromic behavior of organic dyes has never been explored in the pyridinium derivative photochromic system. In this work, two new coordination compounds with a photoactive pyridinium-based inner salt, [Zn(H2O)6](PTA)·(CEbpy)2·2H2O (1, PTA = terephthalate, CEbpy = 1-carboxyethyl-4,4′-bipyridine) and [Zn(H2O)2(CEbpy)2]nBr2n·[Zn(H2O)4(PTA)]n (2), were selected as model compounds for this purpose. Compound 1 features an isolated structure, where uncoordinated photoactive CEbpy ligands connect to hexahydrated zinc ions through hydrogen bonds. Compound 2 features a 1-D chain structure with CEbpy ligands coordinating to zinc ions. Compound 1 shows faster coloration speed upon irradiation than 2, demonstrating that coordination of the electron donor in CEbpy is not in favor of photochromic behavior. Both compounds show significant photoluminescence quenching after coloration, and the intensity contrast before and after coloration for 1 is larger than that for 2. This finding will help to design and synthesize new photochromic compounds with high performance.
Co-reporter:Sheng-Ping Guo, Yang Chi, Guo-Cong Guo
Journal of Alloys and Compounds 2016 Volume 676() pp:101-105
Publication Date(Web):15 August 2016
DOI:10.1016/j.jallcom.2016.02.259
•Single-crystals of ternary selenides Ln2ZrSe5 (Ln = Ce–Nd) were synthesized.•Magnetic susceptibility data were studied.•Comparison between Ln2ZrSe5 and related compounds' crystal structures.•Lanthanide contraction among Ln2ZrSe5 (Ln = La–Nd, Sm, Gd and Tb).Three new ternary rare-earth zirconium chalcogenides, Ce2ZrSe5 (1), Pr2ZrSe5 (2) and Nd2ZrSe5 (3), have been synthesized by a facile solid-state route with boron as the reducing reagent. They crystallize in the space group Pnma of the orthorhombic system, belonging to the U3Se5 structure type. Their 3-D structures are constructed by parallel polyanionic {[ZrSe5]6–}n chains and LnSe8 bicapped trigonal prisms. The magnetic susceptibilities' data indicate their antiferromagnetic-like behavior without magnetic order down to 2 K. The structural relationships among several similar structures are discussed, together with the lanthanide contraction in the Ln2ZrSe5 system.
Co-reporter:Zhi-Qiao Wang, Zhong-Ning Xu, Ming-Jian Zhang, Qing-Song Chen, Yumin Chen and Guo-Cong Guo
RSC Advances 2016 vol. 6(Issue 30) pp:25185-25190
Publication Date(Web):29 Feb 2016
DOI:10.1039/C6RA02929A
High-performance catalysts are the key factor for CO2 activation and conversion. In this paper, we systematically investigate the whole composition evolution process of Cu/SiO2 catalysts for CO2 hydrogenation. The precursor gradually evolved from amorphous Cu species to copper phyllosilicate, then to CuO with the increase of calcination temperature from ambient temperature to 700 °C. With the evolution of the precursor, the corresponding species after reduction were gradually evolved from Cu0 to Cu+, then to Cu0 again. The ratios of Cu+/(Cu+ + Cu0) are positively correlated with the catalytic activities. The Cu+ species derived from copper phyllosilicate were demonstrated to be crucial in achieving high-performance Cu/SiO2 catalysts for CO2 hydrogenation. The composition evolution has been demonstrated to be an efficient strategy to synthesize high-performance catalysts. This strategy of composition evolution can be applied to the synthesis of other high-performance Cu-based heterogeneous catalysts.
Co-reporter:Xiu-Shuang Xing, Zi-Wei Chen, Li-Zhen Cai, Cai Sun, Lin-Rong Cai, Ming-Sheng Wang and Guo-Cong Guo
RSC Advances 2016 vol. 6(Issue 29) pp:24190-24194
Publication Date(Web):26 Feb 2016
DOI:10.1039/C5RA25707G
Long-lived charge-separated states and photoswitchable photoluminescence are important for many photochemical and photophysical applications. Recent studies have demonstrated the effectiveness of MOFs to achieve long-lived charge-separated states; however, the related studies are still rather rare owing to the limited numbers of photoresponsive MOFs. In this work, a new electron-transfer photochromic MOF compound, encapsulating photoactive viologen cations, was found to exhibit a charge-separated state with a lifetime value of more than 2 months, exceeding the reported values of the analogues. In addition, the photochromic process can afford a luminescence contrast up to 10 times between two stable states, which is higher than those of most known pyridine derivative-based photochromic compounds.
Co-reporter:Li-Zhen Cai; Qing-Song Chen; Cui-Juan Zhang; Pei-Xin Li; Ming-Sheng Wang
Journal of the American Chemical Society 2015 Volume 137(Issue 34) pp:10882-10885
Publication Date(Web):August 18, 2015
DOI:10.1021/jacs.5b05320
Polycyanometallate compounds with both photochromism and photomagnetism have appealing applications in optical switches and memories, but such optical behaviors were essentially restricted to the cryogenic temperature. We realized, for the first time, the photochromism and photomagnetism of 3d–4f hexacyanoferrates at room temperature (RT) in [EuIII(18C6)(H2O)3]FeIII(CN)6·2H2O (18C6 = 18-crown-6). Photoinduced electron transfer (PET) from crown to Fe(III) yields long-lived charge-separated species at RT in air in the solid state and also weakens the magnetic susceptibility significantly. The PET mechanism and changing trend of photomagnetism differ significantly from those reported for known 3d–4f hexacyanoferrates. This work not only develops a new type of inorganic–organic hybrid photochromic material but opens a new avenue for RT photomagnetic polycyanometallate compounds.
Co-reporter:Zhi-Qiao Wang, Zhong-Ning Xu, Si-Yan Peng, Ming-Jian Zhang, Gang Lu, Qing-Song Chen, Yumin Chen, and Guo-Cong Guo
ACS Catalysis 2015 Volume 5(Issue 7) pp:4255
Publication Date(Web):June 8, 2015
DOI:10.1021/acscatal.5b00682
Cu-based nanocatalysts have been widely used for CO2 hydrogenation, but their poor stability is the bottleneck for further industrial applications. A high-performance and long-lived Cu/SiO2 nanocatalyst was synthesized by an ammonia-evaporation method for CO2 hydrogenation. The conversion of CO2 reaches up to 28%, which is close to the equilibrium conversion of CO2 (30%), and the selectivity to methanol is 21.3%, which is much higher than the equilibrium selectivity (6.6%) at 320 °C and 3.0 MPa. Furthermore, after 120 h of evaluation, the conversion can be still maintained at a high value (27%), which is much better than a Cu/SiO2 catalyst prepared by traditional impregnation. The Cu+ species has been demonstrated to be the active component for the activation and conversion of CO2. The higher ratio of Cu+/(Cu0 + Cu+) and interaction between the metal and support deriving from copper phyllosilicate are mainly responsible for the high catalytic activity and excellent stability, respectively.Keywords: ammonia-evaporation method; CO2 hydrogenation; copper phyllosilicate; Cu+ species; Cu/SiO2 nanocatalyst
Co-reporter:Guan-E Wang, Gang Xu, Ming-Sheng Wang, Li-Zhen Cai, Wen-Hua Li and Guo-Cong Guo
Chemical Science 2015 vol. 6(Issue 12) pp:7222-7226
Publication Date(Web):17 Sep 2015
DOI:10.1039/C5SC02501J
Single-component white light materials may create great opportunities for novel conventional lighting applications and display systems; however, their reported color rendering index (CRI) values, one of the key parameters for lighting, are less than 90, which does not satisfy the demand of color-critical upmarket applications, such as photography, cinematography, and art galleries. In this work, two semiconductive chloroplumbate (chloride anion of lead(II)) hybrids, obtained using a new inorganic–organic hybrid strategy, show unprecedented 3-D inorganic framework structures and white-light-emitting properties with high CRI values around 90, one of which shows the highest value to date.
Co-reporter:Bin-Wen Liu, Xiao-Ming Jiang, Guan-E Wang, Hui-Yi Zeng, Ming-Jian Zhang, Shu-Fang Li, Wei-Huan Guo, and Guo-Cong Guo
Chemistry of Materials 2015 Volume 27(Issue 24) pp:8189
Publication Date(Web):November 25, 2015
DOI:10.1021/acs.chemmater.5b03649
Co-reporter:Si-Yan Peng, Zhong-Ning Xu, Qing-Song Chen, Zhi-Qiao Wang, Dong-Mei Lv, Jing Sun, Yumin Chen, and Guo-Cong Guo
ACS Catalysis 2015 Volume 5(Issue 7) pp:4410
Publication Date(Web):June 8, 2015
DOI:10.1021/acscatal.5b00365
The catalytic performances of supported Pd nanoparticles (NPs) are strongly dependent on the support materials for CO oxidative coupling to dimethyl oxalate (DMO). Herein, hierarchical flower-like ZnO microspheres composed of porous nanosheets are employed as a new support material for a Pd catalyst, which exhibits excellent catalytic activity for CO oxidative coupling to DMO. The conversion of CO and the selectivity to DMO reach up to 67% and 98% at 130 °C, respectively. Unfortunately, the high activity of Pd/ZnO catalyst gradually deteriorates within 100 h. To resolve the poor stability, we further introduce Mg2+ ions into the ZnO support. It is exciting that the catalytic activity of the Mg2+-doped-ZnO-supported Pd nanocatalyst (Pd/Mg–ZnO) can be maintained for at least 100 h without obvious decay. Catalytic stability is greatly improved by the doping of Mg2+ ions. XRD, UV–visible diffuse reflectance spectra, and high-angle annular dark field scanning transmission electron microscopy characterizations demonstrate that a small portion of Mg2+ ions are successfully incorporated into the lattice of the ZnO support to form a Zn–Mg oxide solid solution. XPS, in situ diffuse reflectance Fourier transform infrared spectroscopy, and H2-temperature-programmed reduction results reveal that the introduction of Mg2+ ions into the ZnO support leads to a strong metal–support interaction caused by electron transfer from the ZnO substrate to the Pd NPs, which can effectively restrain the sintering of the active Pd NPs; retard the growth of Pd NPs; and thus, enhance the catalytic stability.Keywords: CO oxidative coupling; coal to ethylene glycol (CTEG); dimethyl oxalate; Mg2+ doping; Pd/ZnO
Co-reporter:Pei-Xin Li, Ming-Sheng Wang, Li-Zhen Cai, Guan-E. Wang and Guo-Cong Guo
Journal of Materials Chemistry A 2015 vol. 3(Issue 2) pp:253-256
Publication Date(Web):17 Nov 2014
DOI:10.1039/C4TC01315H
Two new isostructural coordination compounds exhibit the rare difunctional properties of both electron-transfer (ET) photochromism and ET thermochromism, which are significantly affected by halogen atoms. The thermocrystallographic studies of the same single crystal have elucidated the electron-donating nature of the halogen atoms.
Co-reporter:Qing-Song Chen, Zhong-Ning Xu, Si-Yan Peng, Yu-Min Chen, Dong-Mei Lv, Zhi-Qiao Wang, Jing Sun, Guo-Cong Guo
Journal of Power Sources 2015 Volume 282() pp:471-478
Publication Date(Web):15 May 2015
DOI:10.1016/j.jpowsour.2015.02.042
•Pd/GNP was synthesized by electrochemical milling method.•Graphite rod is essential for the dissolving of bulk Pd wire.•Pd/GNP was decorated preferentially with (111) faceted Pd nanocrystals.•Pd/GNP exhibited superior activity towards formic acid oxidation.Pd nanocrystals supported on graphene nanoplatelets (Pd/GNP) have been successfully synthesized by simultaneously electrochemical milling of Pd wire and graphite rod. It should be stressed that without the assistance of graphite rod, the Pd nanocrystals are unable to be obtained individually from Pd wire under the same conditions. Investigations of SEM and TEM demonstrate that Pd/GNP are preferentially decorated with (111) faceted nanocrystals. XPS studies confirm the strong metal-support interaction in Pd/GNP and reveal the surface is almost composed of Pd(0) species. Electrochemical measurements show that the prepared Pd based catalyst exhibits superior electrocatalytic activity towards formic acid oxidation, which may be attributed to the combined effects involving the preferentially oriented (111) surface structure, specific electronic structure and high dispersion of Pd nanocrystals as well as the support effects of graphene nanoplatelets. The synthesis method is simple and effective to prepare excellent new carbon-supported electrocatalysts, which is of great significance for direct organic molecule fuel cell.
Co-reporter:Bin-Wen Liu; Hui-Yi Zeng; Ming-Jian Zhang; Yu-Hang Fan; Guo-Cong Guo; Jin-Shun Huang;Zhen-Chao Dong
Inorganic Chemistry 2015 Volume 54(Issue 3) pp:976-981
Publication Date(Web):November 20, 2014
DOI:10.1021/ic502362f
Two new metal sulfides, Ba2Ga8MS16 (M = Si, Ge), have been synthesized by high-temperature solid-state reactions. They are isostructural and crystallize in the noncentrosymmetric space group P63mc (No. 186) with a = 10.866(5) Å, c = 11.919(8) Å, and z = 2 for Ba2Ga8SiS16 (1) and a = 10.886(8) Å, c = 11.915(3) Å, and z = 2 for Ba2Ga8GeS16 (2). Their three-dimensional frameworks are constructed by corner-sharing mixed (Ga/M)S4 (M = Si, Ge) and pure GaS4 tetrahedra, with Ba2+ cations filling in the tunnels. Compounds 1 and 2 are transparent over 0.42–20 μm and have wide band gaps of around 3.4 and 3.0 eV, respectively. Polycrystalline 2 displays strong nonlinear second-harmonic-generation (SHG) intensities that are comparable to that of the benchmark AgGaS2 (AGS) with phase-matching behavior at a laser irradiation of 1950 nm. Of particular interest, compound 2 also possesses a high powder laser-induced damage threshold of ∼22 times that of AGS. The alternate stacking of the mixed (Ga/M)S4 (M = Si, Ge) tetrahedral layer with the pure GaS4 tetrahedral layer along the c axis and the alignment of these two types of tetrahedra in the same direction may be responsible for the large SHG signals observed.
Co-reporter:Dong-Mei Lv, Zhong-Ning Xu, Si-Yan Peng, Zhi-Qiao Wang, Qing-Song Chen, Yumin Chen and Guo-Cong Guo
Catalysis Science & Technology 2015 vol. 5(Issue 6) pp:3333-3339
Publication Date(Web):15 Apr 2015
DOI:10.1039/C5CY00251F
(Pd–CuCl2)/γ-Al2O3 catalyst with excellent activity and selectivity has been successfully developed for vapor-phase carbonylation of methyl nitrite to dimethyl carbonate (DMC). It has been demonstrated that Cl− is necessary for the superior selectivity (99.8%) to DMC, and that Cl− and Cu2+ have a synergetic effect. The Lewis acid sites of the γ-Al2O3 support may be suitable for vapor-phase carbonylation of methyl nitrite to DMC. Moreover, the catalytic mechanism of DMC formation on the (Pd–CuCl2)/γ-Al2O3 catalyst has been reasonably proposed based on the results of XPS and in situ diffuse reflectance infrared spectroscopy. The intermediate Cl–Pd(II)–COOCH3 is the key factor for the synthesis of DMC.
Co-reporter:Yong Liu;Hui-Yi Zeng;Bin-Wen Liu;Geng-E Wang
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 14) pp:2402-2406
Publication Date(Web):
DOI:10.1002/ejic.201500150
Abstract
A new layered compound, Hg5AsS2I3, has been synthesized in the quaternary system mercury/arsenic/chalcogen/halogen by a moderate-temperature solid-state reaction. The compound crystallizes in the space group C2/c of the monoclinic system, and its structure consists of ∞1[Hg(1)2Hg(2)2As2/2S2] eight-membered-ring chains bridged by Hg atoms to form [Hg(1)2Hg(2)2Hg(3)As2/2S2] layers with inner- and interlayer electrostatic interactions between I and Hg. The optical properties were investigated by means of diffuse reflectance and FTIR spectra. The electronic band structures, along with density of states (DOS) calculations by DFT, indicate that the title compound is a semiconductor, and its optical absorption mainly leads to charge transitions from I-5p, As-4p and S-3p states to Hg-6s states, and both I(1) and I(2) atoms contribute to the top of the valence bands.
Co-reporter:Sheng-Ping Guo and Guo-Cong Guo
Journal of Materials Chemistry A 2014 vol. 2(Issue 48) pp:20621-20628
Publication Date(Web):17 Oct 2014
DOI:10.1039/C4TA04757E
The ternary dysprosium sulfur telluride Dy4S4Te3 was synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the monoclinic space group C2/m with a = 6.720 (1), b = 13.748 (2), c = 6.715 (1) Å and β = 103.36 (1)°, belongs to the Ho4S4Te2.68 structure type, and its 3-D structure features 2-D ladder-like (DyS)n layers linked by Dy–Te1 and Dy–Te2 bonds with additional Te1–Te1 dumbbells. The (DyS)n layers and the (DyQ)n (Q = S, Se and Te) layers in other binary Dy–Q compounds are compared. Measurement of it magnetic susceptibility shows its paramagnetic behavior. The investigation of its optical properties indicates that it has an energy gap of 1.43 eV, which is also verified by the electronic band structure calculation via the Vienna ab initio simulation package (VASP). The photocatalytic behavior of the polycrystalline powder sample investigated by decomposing rhodamine B under halogen lamp irradiation indicates that its photocatalytic activity can be comparable to that of Degussa P25 TiO2.
Co-reporter:Yumin Chen, Qing-Song Chen, Si-Yan Peng, Zhi-Qiao Wang, Gang Lu and Guo-Cong Guo
Chemical Communications 2014 vol. 50(Issue 14) pp:1662-1664
Publication Date(Web):21 Nov 2013
DOI:10.1039/C3CC47567K
Manipulating the degrees of concavity or Miller indices of high-index facets is significant for metal nanocrystals to further tailor their properties; however, generating a concave surface with negative curvature is still in the early development stage and tuning the degree of concavity remains a challenge. Herein, we have developed a simple and effective site-selective etching strategy to manipulate the concavity of rhodium (Rh) nanocrystals with high-index facets.
Co-reporter:Si-Yan Peng, Zhong-Ning Xu, Qing-Song Chen, Zhi-Qiao Wang, Yumin Chen, Dong-Mei Lv, Gang Lu and Guo-Cong Guo
Catalysis Science & Technology 2014 vol. 4(Issue 7) pp:1925-1930
Publication Date(Web):16 Apr 2014
DOI:10.1039/C4CY00245H
Pd/MgO catalysts are found, for the first time, to be extraordinarily active and stable for CO oxidative coupling to dimethyl oxalate. A series of Pd/MgO catalysts with Pd loadings of 0.1, 0.3, 0.5, 1 and 2 wt% were prepared by a wet impregnation method and systematically characterized by XRD, TEM, ICP, UV-DRS, H2-TPR and CO2-TPD. It has been demonstrated that the amount of Pd loading has a pronounced effect on the catalytic activity for CO oxidative coupling to dimethyl oxalate. CO conversion increases with the increase of the Pd loading due to high dispersion and similar sizes of Pd nanoparticles, as well as, the increase in number of surface active sites.
Co-reporter:Rong-Guang Lin, Gang Xu, Gang Lu, Ming-Sheng Wang, Pei-Xin Li, and Guo-Cong Guo
Inorganic Chemistry 2014 Volume 53(Issue 11) pp:5538-5545
Publication Date(Web):May 20, 2014
DOI:10.1021/ic5002144
Two new member of (V)(2n+2)/2[Bi2nCl8n+2] series hybrids, (BzV)2[Bi2Cl10] (1) and (BzV)5[Bi3Cl14]2·(C6H5CH2)2O (2) (where BzV2+ = N,N′-dibenzyl-4,4′-bipyridinium and (C6H5CH2)2O = dibenzyl ether) have been obtained, and compound 2 contains an unprecedented discrete trimer [Bi3Cl14]5– counterion. The novel in situ-synthesized symmetric viologen cation with aromatic groups on both sides of 4,4′-bipy would provide more opportunities to create π···π interactions to optimize the photochromic property of the hybrid, and different bismuthated-halide oligomers enable us to discuss the size effect in this series of compounds. Both 1 and 2 are photochromic, and their photoresponsive rate is faster than that of reported viologen–metal halide hybrids. Experimental and theoretical data illustrated that the size of the inorganic oligomer can significantly influence the photoresponsive rate of the viologen dication, and the π···π interaction behaves as not only a powerful factor to stabilize the viologen monocation radical but also the second electron-transfer pathway, from a π-conjugated substituent to a viologen cation, for the photochromic process.
Co-reporter:Cui-Juan Zhang, Zi-Wei Chen, Rong-Guang Lin, Ming-Jian Zhang, Pei-Xin Li, Ming-Sheng Wang, and Guo-Cong Guo
Inorganic Chemistry 2014 Volume 53(Issue 2) pp:847-851
Publication Date(Web):December 23, 2013
DOI:10.1021/ic402182j
The model compound [Zn(HCOO)2(4,4′-bipy)] (1; 4,4′-bipy = 4,4′-bipyridine) is selected in this work to demonstrate the effectiveness of our previously proposed design strategy for electron-transfer photochromic metal–organic complexes. The electron-transfer photochromic behavior of 1 has been discovered for the first time. Experimental and theoretical data illustrate that the photochromism of 1 can be attributed to the electron transfer from formato to 4,4′-bipy and the formation of a radical photoproduct. The electron transfer prefers to occur between formato and 4,4′-bipy, which are combined directly by the Zn(II) atoms. A high-contrast (up to 8.3 times) photoluminescence switch occurs during the photochromic process. The similarity of photochromic behaviors among 1 and its analogues as well as viologen compounds has also been found. Photochromic studies of this model compound indicate that new electron-transfer photochromic metal–organic complexes can be largely designed and synthesized by the rational assembly of nonphotochromic electron-donating and electron-accepting ligands.
Co-reporter:Jin-Shuang Guo, Gang Xu, Xiao-Ming Jiang, Ming-Jian Zhang, Bin-Wen Liu, and Guo-Cong Guo
Inorganic Chemistry 2014 Volume 53(Issue 9) pp:4278-4280
Publication Date(Web):April 14, 2014
DOI:10.1021/ic500315z
A 3D metal–organic framework (MOF), [Zn(BPHY)(SA)]n (1; BPHY = 1,2-bis(4-pyridyl)hydrazine, H2SA = succinic acid), which crystallizes in a noncentrosysmmetric space group (Cc), has been solvothermally obtained and testified to be a good nonlinear-optical material with the largest second-harmonic-generation response among the known MOFs based on sysmmetric ligands and high stability. Ultraviolet-to-visible tunable emission for 1 is observed.
Co-reporter:Guang-Ning Liu, Guo-Cong Guo, Ming-Sheng Wang and Jin-Shun Huang
Dalton Transactions 2014 vol. 43(Issue 10) pp:3931-3938
Publication Date(Web):03 Jan 2014
DOI:10.1039/C3DT53515K
Two novel manganese thioarsenates, {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 (1, 2,2′-bipy = 2,2′-bipyridine) and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2′-bipy complex cations were synthesized. They feature two terminal [Mn(2,2′-bipy)2(SCN)]+ complex cations bridged by a polyanion {[Mn(2,2′-bipy)]2(AsVS4)2}2− for 1 and a cyclic thioarsenate anion (AsIII2S6)2− for 2. In 2, the [AsIII2(S2)2S2]2− anion can be described as two (AsIIIS3)3− trigonal-pyramids interlinked through S–S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between MnII centers in the two compounds.
Co-reporter:Zi-Wei Chen, Gang Lu, Pei-Xin Li, Rong-Guang Lin, Li-Zhen Cai, Ming-Sheng Wang, and Guo-Cong Guo
Crystal Growth & Design 2014 Volume 14(Issue 5) pp:2527-2531
Publication Date(Web):April 10, 2014
DOI:10.1021/cg500239p
We have studied the electron-transfer photochromism of the crystalline adducts of 4,4′-bipyridine (Bpy) and carboxylic acids and revealed the key structural parameters that decide whether the photochromism can happen for the first time. Experimental and theoretical analyses on nine known examples showed that the hydrogen bonds, instead of π–π stacking interactions, are the defining factor to the photochromism. Only the presence of N–H···O hydrogen bonds can fulfill the electron transfer from the carboxylate group to the Bpy part, although both the N···O separations of O–H···N and N–H···O hydrogen bonds are suitable for the so-called through-space electron transfer. These results can not only help to screen out the photochromic species from the known hundreds of Bpy–carboxylic acid adducts deposited in the Cambridge Crystallographic Data Centre (CCDC) database but also guide the design and syntheses of new adducts using diverse N-heterocyclic aromatic molecules and carboxylic acids.
Co-reporter:Jing Sun, Yumin Chen, Zhong-Ning Xu, Qing-Song Chen, Guan-E Wang, Ming-Jian Zhang, Gang Lu, Ke-Chen Wu and Guo-Cong Guo
CrystEngComm 2014 vol. 16(Issue 30) pp:6823-6826
Publication Date(Web):27 May 2014
DOI:10.1039/C4CE00608A
The rational design and synthesis of ternary two-dimensional alloy nanocrystals with a non-layered structure are still a challenge. Here, we show, for the first time, the synthesis of homogeneous ternary ZnS1−xSex nanosheets by thermal decomposition of lamellar inorganic–organic hybrid precursors. The morphology, composition and crystal structure of ZnS1−xSex nanosheets have been thoroughly investigated. We also found that the lattice constants and bandgaps of ZnS1−xSex nanosheets could be easily tuned via alteration of the Se/S ratio. Our work provides a facile and effective strategy to synthesize homogeneous multinary non-layered chalcogenide nanosheets with tunable compositions and bandgaps.
Co-reporter:Jin-Shuang Guo, Gang Xu, Shuai-Hua Wang, Ming-Sheng Wang, Ming-Jian Zhang, Guo-Cong Guo, Jin-Shun Huang
Inorganic Chemistry Communications 2014 Volume 45() pp:108-111
Publication Date(Web):July 2014
DOI:10.1016/j.inoche.2014.04.011
•We report a non-interpenetrated 2D zinc compound based on saturated fatty acid.•This compound exhibits tunable blue emission excited by UV light.•The luminescent mechanism of this compound has been studied theoretically.We report a new non-interpenetrated 2D zinc coordination polymer, [Zn(AA)(BPHY)]n (1) (H2AA = adipic acid, BPHY = 1,2-bis(4-pyridyl)hydrazine), which is a mixed ligand complex. The solid-state sample of 1 exhibits tunable blue emission excited by UV light with the wavelengths from 320 nm to 380 nm. The luminescent mechanism of 1 has been studied by theoretical calculation.A new non-interpenetrated zinc coordination polymer based on saturated fatty acid ligand can display blue emission excited by UV light.
Co-reporter:Dr. Feng Luo;Dr. Cong Bin Fan;Ming Biao Luo;Dr. Xiao Liu Wu;Yan Zhu;Shou Zhi Pu;Wen-Yuan Xu;Dr. Guo-Cong Guo
Angewandte Chemie International Edition 2014 Volume 53( Issue 35) pp:9298-9301
Publication Date(Web):
DOI:10.1002/anie.201311124
Abstract
We demonstrate herein a promising pathway towards low-energy CO2 capture and release triggered by UV and visible light. A photosensitive diarylethene ligand was used to construct a photochromic diarylethene metal–organic framework (DMOF). A local photochromic reaction originating from the framework movement induced by the photoswitchable diarylethene unit resulted in record CO2-desorption capacity of 75 % under static irradiation and 76 % under dynamic irradiation.
Co-reporter:Dr. Pei-Xin Li;Dr. Ming-Sheng Wang;Dr. Ming-Jian Zhang;Dr. Chen-Sheng Lin;Li-Zhen Cai;Sheng-Ping Guo ;Dr. Guo-Cong Guo
Angewandte Chemie International Edition 2014 Volume 53( Issue 43) pp:11529-11531
Publication Date(Web):
DOI:10.1002/anie.201406554
Abstract
The first bulk electron-transfer photochromic compound with intrinsic second-order nonlinear optical (NLO) photoswitching properties has been synthesized. This system employs an electron-transfer photoactive asymmetric viologen ligand coordinated to a zinc(II) center.
Co-reporter:Zhong-Ning Xu, Jing Sun, Chen-Sheng Lin, Xiao-Ming Jiang, Qing-Song Chen, Si-Yan Peng, Ming-Sheng Wang, and Guo-Cong Guo
ACS Catalysis 2013 Volume 3(Issue 2) pp:118
Publication Date(Web):December 20, 2012
DOI:10.1021/cs300759h
We synthesized monodisperse Pd nanocrystals with exposed (111) and (100) facets through preferentially oriented facet growth technology. We then supported them on α-Al2O3 as catalysts for application in CO oxidative coupling to dimethyl oxalate (DMO) and find, for the first time, that the (111) facets of Pd nanocrystals are active planes for CO oxidative coupling to DMO. This conclusion is based on experiment results, reaction mechanism, and density functional theory calculation. Directed by this shape effect, a high-performance and long-lived nanocatalyst with much lower Pd load for CO oxidative coupling to DMO was successfully prepared by a new wet impregnation–solution chemical reduction method, which can well control the exposure of (111) facets and sizes of Pd nanocrystals.Keywords: CO oxidative coupling to dimethyl oxalate; Pd nanocatalyst; shape effect; wet impregnation−solution chemical reduction method
Co-reporter:Ming-Jian Zhang, Xiao-Ming Jiang, Liu-Jiang Zhou and Guo-Cong Guo
Journal of Materials Chemistry A 2013 vol. 1(Issue 31) pp:4754-4760
Publication Date(Web):04 Jun 2013
DOI:10.1039/C3TC30808A
Two phases of Ga2S3 with different space groups Cc and F3m were synthesized in pure phase by a facile boron–sulfur–metallic oxide reaction. They both have a good transparency in the wavelength range of 0.44–25 μm and exhibit comparatively large second-harmonic generation (SHG) effects of about 0.7 and 0.5 times that of commercial KTiOPO4 (KTP), for the monoclinic and cubic Ga2S3 respectively. The monoclinic Ga2S3 is phase-matchable at the wavelength of 1910 nm while the cubic phase is non-phase-matchable. In order to study their powder laser induced damage threshold (LIDT) properties, a single pulse powder LIDT measurement method was proposed and it was found that they have very high powder LIDTs of about 30 and 100 times that of AgGaS2 (AGS), respectively for the monoclinic and cubic phase, under a single pulse 1064 nm laser radiation with a pulse width τp of 8 ns. To gain further insights into the nonlinear optical (NLO) and LIDT properties of the monoclinic and cubic Ga2S3, calculations of second-order NLO susceptibility and lattice energy density (LED) were also performed to explain their SHG efficiencies and high LIDTs.
Co-reporter:Si-Yan Peng, Zhong-Ning Xu, Qing-Song Chen, Yu-Min Chen, Jing Sun, Zhi-Qiao Wang, Ming-Sheng Wang and Guo-Cong Guo
Chemical Communications 2013 vol. 49(Issue 51) pp:5718-5720
Publication Date(Web):22 Mar 2013
DOI:10.1039/C3CC00219E
A Pd/α-Al2O3 nanocatalyst with ultra-low Pd loading exhibits high activity and stability for CO oxidative coupling to dimethyl oxalate, which was prepared by a Cu2+-assisted in situ reduction method at room temperature. The small size and high dispersion of Pd nanoparticles facilitated by Cu2+ ions are responsible for the excellent catalytic activity.
Co-reporter:Rong-Guang Lin, Gang Xu, Ming-Sheng Wang, Gang Lu, Pei-Xin Li, and Guo-Cong Guo
Inorganic Chemistry 2013 Volume 52(Issue 3) pp:1199-1205
Publication Date(Web):January 16, 2013
DOI:10.1021/ic301181b
A series of inorganic–organic hybrid compounds L2(Bi2Cl10) (L = HMV2+ = N-proton-N′-methyl-4,4′-bipyridinium for 1, L = HBzV2+ = N-proton-N′-benzyl-4,4′-bipyridinium for 2, and L = HPeV2+ = N-proton-N′-phenethyl-4,4′-bipyridinium for 3) have been successfully synthesized by an in situ solvothermal reaction. Compounds 1–3, with the same metal halide as anions but different asymmetric viologen molecules as cations, are ideal model compounds for investigating the detailed effect of different photochromically active molecules on the photochromic properties of the hybrids. Compound 1 shows no photochromic behavior, but compounds 2 and 3 possess photochromism and show a faster photoresponse rate than other reported viologen metal halide hybrids. Studies on the relationship between the structure and photochromic behavior clearly reveal that π-conjugated substituents could be used to improve the photoresponsibility and enrich the developed color efficiently and that the π···π interaction among organic components may not only be a powerful factor to stabilize the viologen monocation radical but also act as the second path of electron transfer from the π-conjugated substituent to the viologen cation for the photochromic process, which significantly influences the photochromic properties.
Co-reporter:Xiao-Ming Jiang, Guan-E Wang, Zhi-Fa Liu, Ming-Jian Zhang, and Guo-Cong Guo
Inorganic Chemistry 2013 Volume 52(Issue 15) pp:8865-8871
Publication Date(Web):July 9, 2013
DOI:10.1021/ic401056t
Two new different-bond-type hybrid compounds, (Hg6P4Cl3)(PbCl3) (1) and (Hg23P12)(ZnCl4)6 (2), with supramolecular interactions between host and guest moieties, which based on metal–pnicogen, pnicogen–pnicogen, and metal–halogen bonds were obtained by solid-state reactions. Compounds 1 and 2 show large second-harmonic-generation (SHG) activity and are transparent in the wide mid-IR region, providing an effective route for searching new IR nonlinear-optical material systems by combining two or more different bond types with no IR absorption within a single compound through supramolecular assembly. Theory predications based on first-principles calculations are also performed on the SHG properties of 1 and 2.
Co-reporter:Jin-Shuang Guo, Gang Xu, Guo-Cong Guo, and Jin-Shun Huang
Crystal Growth & Design 2013 Volume 13(Issue 6) pp:2642-2649
Publication Date(Web):April 19, 2013
DOI:10.1021/cg400394d
Five coordination polymers 1–5 with four types of (4,4) layers have been synthesized through a new strategy of designing their crystal structures based on (4,4) topology. Compound [Co(adc)(bpp)(H2O)]n (1) presents a 2-D structure with 2-fold homointerpenetration of layer A, while the 2-D compound {[Ni(adc)(bpp)2(H2O)]2·bpp}n (2) presents 2-fold heterointerpenetration of layer B and layer C. Compound [Zn(adc)(bpp)·DMF]n (3) displays a typical 2-D → 3-D parallel interpenetrating structure of layer D. Compounds [Ni(Cladc)(bpp)(H2O)]n (4) and [Co(Cladc)(bpp)(H2O)]n (5) are isomorphous and display similar structures to 1. (H2adc = 4,4′-azodibenzoic acid, ClH2adc = 3,3′-dichloro-4,4′-azodibenzoic acid, bpp = 1,3-di(4-pyridyl)propane, DMF = N,N-dimethylformamide). Luminescence properties and thermal stabilities of 1–5 have been explored.
Co-reporter:Xiao-Ming Jiang, Xiao-Guo Li, Yu-Hang Fan, Bin-Wen Liu, Hui-Yi Zeng and Guo-Cong Guo
Dalton Transactions 2013 vol. 42(Issue 43) pp:15475-15481
Publication Date(Web):11 Sep 2013
DOI:10.1039/C3DT51451J
Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy.
Co-reporter:Ming-Jian Zhang, Bing-Xuan Li, Bin-Wen Liu, Yu-Hang Fan, Xiao-Guo Li, Hi-Yi Zeng and Guo-Cong Guo
Dalton Transactions 2013 vol. 42(Issue 39) pp:14223-14229
Publication Date(Web):17 Jul 2013
DOI:10.1039/C3DT51139A
Two new ternary rare earth chalcogenides, Dy3GaS6 (1) and Y3GaS6 (2), are reported here. They both crystallize in the orthorhombic space group Cmc21 (no. 36). Both are synthesized in pure phase and show phase-matchable second harmonic generation (SHG) of about 0.2 and 0.5 times, respectively for 1 and 2, as strong as that of KTiOPO4 (KTP) based on the powder SHG measurement at the wavelength of 1910 nm. They possess high powder laser induced damage thresholds (LIDTs), respectively, about 14 and 18 times that of AgGaS2 (AGS) based on the powder LIDT measurements under 1064 nm laser irradiation. They both exhibit wide transparency in the IR region (2.5–25 μm). It is believed that the title compounds are new candidates for nonlinear optical (NLO) materials in the IR region. To gain further insights into the NLO and LIDT properties of 1 and 2, the calculations of second-order NLO susceptibility and lattice energy density (LED) were also performed to explain their SHG efficiencies and high LIDTs.
Co-reporter:Sheng-Ping Guo, Guan-E Wang, Ming-Jian Zhang, Mei-Feng Wu, Guang-Ning Liu, Xiao-Ming Jiang, Guo-Cong Guo and Jin-Shun Huang
Dalton Transactions 2013 vol. 42(Issue 8) pp:2679-2682
Publication Date(Web):19 Dec 2012
DOI:10.1039/C2DT32321D
A series of rare-earth zirconium chalcogenides Ln2ZrQ5 (Ln = La, Sm, Gd; Q = S, Se) synthesized by using boron as the reducing reagent show unprecedented single-crystal's intrinsic voltage-dependent effects and order antiferromagnetically.
Co-reporter:Li-Zhen Cai, Ming-Sheng Wang, Shuai-Hua Wang, Pei-Xin Li, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2013 vol. 15(Issue 38) pp:7670-7679
Publication Date(Web):24 Jul 2013
DOI:10.1039/C3CE41050A
A series of one-dimensional (1-D) N-succinopyridine-based complexes: [Cu(L−)(H2O)2]Cl·2H2O (1), [Pr(L−)(H2O)4]Cl2 (2), [Ln(L−)(H2O)5]Cl2·3H2O (Ln = Eu (3), Gd (4)), and [Er(L−)(H2O)4]Cl2·H2O (5) (HL = N-succinopyridine (−OOC–CH(N+C5H5)–CH2–COOH)) have been prepared and characterized by single-crystal X-ray diffraction. The frameworks of complexes 1, 2 and 5 constructed from dinuclear metal building blocks exhibit 1-D double-strand loop-like chains; these chains are further connected to each other by hydrogen bonds forming a 3-D supramolecular architecture. Whereas complexes 3 and 4 feature hydrogen bonding 2-D supramolecular networks assembled from 1-D chains that are constructed from mononuclear metal building blocks. The effects of different metal ions, steric hindrance and coordination diversities of HL on the polymeric architectures have been discussed. In addition, thermogravimetric and magnetic properties of these complexes were also investigated in this paper.
Co-reporter:Guan-E Wang, Gang Xu, Pei-Xin Li, Shuai-Hua Wang, Ming-Sheng Wang, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2013 vol. 15(Issue 14) pp:2579-2582
Publication Date(Web):29 Jan 2013
DOI:10.1039/C3CE40136G
A novel inorganic–organic hybrid [Cu(2,2′-bipy)2I]2n(PbI3)2n·nDMF·nH2O (1), which exhibits diplex single-crystal-to-single-crystal transformation, can transform to a guest molecule released compound [Cu(2,2′-bipy)2I]n(PbI3)n (1a) by thermal induction, or to both a guest molecule released and ligand exchanged compound [Cu(2,2′-bipy)3]n(Pb2I6)n (1b) by solvent induction.
Co-reporter:Jian-Di Lin, Shuai-Hua Wang, Li-Zhen Cai, Fa-Kun Zheng, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2013 vol. 15(Issue 5) pp:903-910
Publication Date(Web):12 Nov 2012
DOI:10.1039/C2CE26213D
Hydrothermal reaction of cadmium salts with HATZ in the presence of R4NBr (R = Et, Pr) led to two organic cation templated Cd(II) MOFs, (Et4N)[Cd6Br5(ATZ)8]·H2O (1) and (Pr4N)[Cd4Br5(ATZ)4] (2) (HATZ = 5-amino-tetrazolate, Et = ethyl and Pr = propyl), which are the first examples of tetraalkylammonium cations templated N-heterocyclic ligand based MOFs. These two MOFs have been fully characterized by single crystal X-ray diffraction, XRD, TGA, IR, elemental analysis, photoluminescence spectra and combustion heat measurement. The anionic frameworks of 1 and 2 are three- and two-dimensional, respectively. Topological analyses show that compound 1 exhibits an unprecedented binodal (4,10)-connected network, which is a subnet of the (12,12)-connected tcj net, and compound 2 is a 2-D uninodal four-connected network when the Cd6 clusters in these two MOFs are viewed as nodes. Moreover, compound 1 maybe have potential application as an energetic material due to its high enthalpy of formation.
Co-reporter:Xiao-Guo Li;Xiao-Ming Jiang;Ming-Jian Zhang;Bin-Wen Liu;Yu-Hang Fan;Jin-Shun Huang
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 35) pp:5980-5986
Publication Date(Web):
DOI:10.1002/ejic.201300888
Abstract
Four new inorganic supramolecular complexes, [Hg4P2][ZrCl6] (1), [Hg4As2][ZrCl6] (2), [Hg4P2][HfCl6] (3), and [Hg4As2][HfCl6] (4), have been prepared by moderate-temperature solid-state reactions. All compounds crystallize in the space group Pbca of the orthorhombic system with Z = 8. Their structures are built up of mercury pnictide cationic hosts and distorted octahedral [MCl6]2– (M = Zr, Hf) guests. The isolated octahedral guests consist of tetravalent Zr4+ and Hf4+ cations coordinated by chlorine atoms and are embedded in the infinite channels formed by the host framework. Their optical properties were investigated in terms of their diffuse reflectance and FTIR spectra. The electronic band structures along with densities of states (DOS) calculated by DFT indicate that all of the title compounds are semiconductors with direct band gaps, and their optical absorptions mainly originate from charge transitions from Cl 3p and P 3p/As 4p states to Hg 6s, Hg 5p, and Zr 4d/Hf 5d states. Optical dielectric constant calculations show that 1–4 possess dielectric anisotropy, which is consistent with their structural studies.
Co-reporter:Cui-Juan Zhang, Ming-Sheng Wang, Guo-Cong Guo
Inorganic Chemistry Communications 2013 Volume 35() pp:76-78
Publication Date(Web):September 2013
DOI:10.1016/j.inoche.2013.05.032
•A new Ag(I)-carboxylate complex with intense yellowish green phosphorescence•The π-conjugated ancillary ligand significantly influences the photoluminescence.•Propose a luminescence mechanism based on the experimental and theoretical dataReaction of the 2-D MOF [AgL]n·nH2O (1; L = 4-cyanobenzoate) with pyrazine (L′) in water yielded [Ag2L2L′]n·2nH2O (2) with a chain-like structure. Compound 1 features tunable yellow-to-white photoluminescence when its wavelength of excitation light varies. The photoluminescence of 2 obviously differs from that of 1: the former displays intense yellowish green phosphorescence with a shorter lifetime of ~ 3.58 μs and an unresolved peak shape, and does not exhibit tunable photoluminescence upon irradiation of 280–380 nm UV light. Electron transition from the [Ag2(COO)2] cluster to pyrazine is probably responsible for the phosphorescence of 2 based on the experimental and theoretical results.Reaction of the 2-D MOF [Ag(4-cyanobenzoate)]n·nH2O (1) with pyrazine in water yielded [Ag2(4-cyanobenzoate)2(pyrazine)]n·2nH2O (2) with a chain-like structure. Compound 1 features tunable yellow-to-white photoluminescence, while compound 2 only displays yellowish green phosphorescence. The luminescence mechanism of 1 clearly differs from that of 2.
Co-reporter:Guan-E Wang, Gang Xu, Ming-Sheng Wang, Jing Sun, Zhong-Ning Xu, Guo-Cong Guo and Jin-Shun Huang
Journal of Materials Chemistry A 2012 vol. 22(Issue 33) pp:16742-16744
Publication Date(Web):09 Jul 2012
DOI:10.1039/C2JM32830E
A novel inorganic–organic hybrid (H2DAB)(Pb2I6)·2H2O, is employed as a new nitrite detection reagent with extremely high sensitivity and selectivity, in which the organic component features dual functions that afford a self-supplied acidic environment and act as a reagent for spectrophotometrically detecting nitrite anions. This new nitrite detection reagent effectively simplifies the test procedure and can be used to qualitatively distinguish nitrites with the naked eye in rural and remote areas.
Co-reporter:Feng Luo, Ming-Sheng Wang, Ming-Biao Luo, Gong-Ming Sun, Yu-Mei Song, Pei-Xin Li and Guo-Cong Guo
Chemical Communications 2012 vol. 48(Issue 48) pp:5989-5991
Publication Date(Web):24 Apr 2012
DOI:10.1039/C2CC32103C
This work presents a prototype of chiral porous metal–organic framework with the porous wall decorated by different functional groups. The special structure in conjunction with the gas adsorption results reveals some relationship between CO2 adsorption and functional points. Moreover, outstanding tunable photoluminescence and direct white-light emission is observed.
Co-reporter:Guang-Ning Liu, Guo-Cong Guo, Feng Chen, Shuai-Hua Wang, Jing Sun, and Jin-Shun Huang
Inorganic Chemistry 2012 Volume 51(Issue 1) pp:472-482
Publication Date(Web):December 8, 2011
DOI:10.1021/ic201932z
The exploration in two hydro(solvo)thermal reaction systems As/S/Mn2+/phen/methylamine aqueous solution and As/S/Mn2+/2,2′-bipy/H2O affords five new manganese thioarsenates with diverse structures, namely, (CH3NH3){[Mn(phen)2](AsVS4)}·phen (1 and 1′), (CH3NH3)2{[Mn(phen)]2(AsVS4)2} (2), {[Mn(phen)2](AsIII2S4)}n (3), {[Mn(phen)]3(AsIIIS3)2}·H2O (4), and {[Mn(2,2′-bipy)2]2(AsVS4)}[AsIIIS(S5)] (5). Compound 1 comprises a {[Mn(phen)2](AsVS4)}− complex anion, a monoprotonated methylamine cation and a phen molecule. Compound 2 contains a butterfly like {[Mn(phen)]2(AsVS4)2}2– anion charge compensated by two monoprotonated methylamine cations. Compound 3 is a neutral chain formed by a helical 1∞(AsIIIS2–) vierer chain covalently bonds to [MnII(phen)]2+ complexes via all its terminal S atoms. Compound 4 features a neutral chain showing the stabilization of noncondensed (AsIIIS3)3– anions in the coordination of [MnII(phen)]2+ complex cations. Compound 5 features a mixed-valent AsIII/AsV character and an interesting chalcogenidometalates structure, where a polycation formed by the connection of two [Mn(2,2′-bipy)2]2+ complex cation and a (AsVS4)3– anion acts as a countercation for a polythioarsenate anion, [AsIIIS(S5)]−. The title compounds exhibit optical gaps in the range 1.58–2.48 eV and blue photoluminescence. Interestingly, compound 1 displays a weak second harmonic generation (SHG) response being about 1/21 times of KTP (KTiOPO4). Magnetic measurements show paramagnetic behavior for 1 and dominant antiferromagnetic behavior for 2–5. Of particular interest is 4, which is the first manganese chalcogenide showing spin-canting characteristic.
Co-reporter:Xiang-Ying Lv ; Ming-Sheng Wang ; Chen Yang ; Guan-E Wang ; Shuai-Hua Wang ; Rong-Guang Lin
Inorganic Chemistry 2012 Volume 51(Issue 7) pp:4015-4019
Publication Date(Web):March 12, 2012
DOI:10.1021/ic2020868
Photochromism of N-methyl-4,4′-bipyridinium (MQ+) salts and their metal complexes has never been reported. A series of MQ+ coordinated halozinc complexes [(MQ)ZnX3] (X = Cl (1), Br (2), I (3)) and [(MQ)ZnCl1.53I1.47]2(MQ)ZnCl1.68I1.32 (4), with better physicochemical stability than halide salts of the MQ+ cation, have been found to exhibit different photochromic behaviors. Compounds 1–3 are isostructural, but only 1 and 2 show photochromism. Introduction of partial Cl atoms to nonphotochromic compound 3 yields compound 4, which also displays photochromism. The photochromic response of 1, 2, and 4 indicates the presence of their long-lived charge separation states, which originate from X → MQ+ electron transfer according to ESR and XPS measurements. Studies on the influence of different coordinated halogen atoms demonstrate that the Cl atom may be a more suitable electron donor than Br and I atoms to design redox photochromic metal complexes.
Co-reporter:Li-Zhen Cai, Ming-Sheng Wang, Ming-Jian Zhang, Guan-E Wang, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2012 vol. 14(Issue 19) pp:6196-6200
Publication Date(Web):18 Jun 2012
DOI:10.1039/C2CE25755F
Two fluorescent cadmium complexes, [HL][CdCl2(H2O)2] (1) and [HL][CdBr2(H2O)2] (2) (HL = N-succinopyridine), have been prepared and characterized by single-crystal X-ray diffraction. Complex 1 contains a unique μ2-Cl bridged neutral 2D inorganic layer, which is further connected to isolated HL molecules by hydrogen bonds forming a hamburger-like OIO 2D supramolecular architecture. Complex 2 features a 3D supramolecular network assembly from 1D inorganic chains and discrete organic molecules through hydrogen bonds. Thermogravimetric, luminescent properties and theoretical calculations of 1 and 2 are also discussed. Moreover, UV-to-Vis tunable emissions for N-succinopyridine and 1 as well as blue-to-green tunable emission for 2 are observed.
Co-reporter:Guan-E Wang, Ming-Sheng Wang, Ming-Jian Zhang, Li-Zhen Cai, Bin-Wen Liu, Cui-Juan Zhang, Guo-Cong Guo, Jin-Shun Huang
Inorganic Chemistry Communications 2012 Volume 23() pp:137-141
Publication Date(Web):September 2012
DOI:10.1016/j.inoche.2012.07.009
Inorganic–organic hybrids with mixed halo atoms or organically coordinated halometal-complex cations are rare. A series` of haloplumbate hybrids with these structural features, [Cu(phen)2Cl]n(PbCl3)n (phen = 1,10-phenanthroline) (1), [Cu(phen)2Cl]n[PbClI(Cl0.5I0.5)]n (2), and [Cu(phen)2I]n(PbI3)n (3), have been solvothermally synthesized using phen coordinated halocopper(II) complexes as templates and balance cations. Their haloplumbate ions all show 1-D chain structures. Compounds 1–3 feature the hybridization of inorganic–organic hybrids: 1) their absorption edges fall in the range of those of semiconductors, which is typical for bulk lead(II) halides, but show a red shift compared with those of the latter; 2) bulk lead(II) halides are nonluminous upon UV irradiation, but introduction of the phen coordinated halocopper(II) complexes as templates enable the hybrids to emit blue light. Their luminescent intensities gradually decrease with the increase of I content, which indicates the potential to design and syntheses of new luminescent halide materials by means of variation of halo atoms and that iodoplumbates are not good candidates for luminescent materials.Inorganic–organic hybrids with mixed halo atoms or organic coordinated halometal-complex cations are rare. The title compounds with such structural characters feature the hybridization of inorganic–organic hybrids: 1) their absorption edges fall in the range of those of semiconductors, which is typical for bulk lead(II) halides, but show a red shift compared with those of the latter; 2) bulk lead(II) halides are nonluminous upon UV irradiation, but introduction of the phen coordinated halocopper(II) complexes as templates enable the hybrids to emit blue light.Highlights► Study the effect of organically coordinated halometal-complex cations templates on structures ► Novel haloplumbates with organically coordinated halometal complexes as templates and mixed halo atoms ► Study the influence of different I content on photoluminescence
Co-reporter:Ming-Sheng Wang;Chen Yang;Guan-E. Wang;Gang Xu;Xiang-Ying Lv;Zhong-Ning Xu;Rong-Guang Lin;Li-Zhen Cai ;Dr. Guo-Cong Guo
Angewandte Chemie International Edition 2012 Volume 51( Issue 14) pp:3432-3435
Publication Date(Web):
DOI:10.1002/anie.201108220
Co-reporter:Ming-Sheng Wang;Chen Yang;Guan-E. Wang;Gang Xu;Xiang-Ying Lv;Zhong-Ning Xu;Rong-Guang Lin;Li-Zhen Cai ;Dr. Guo-Cong Guo
Angewandte Chemie 2012 Volume 124( Issue 14) pp:3488-3491
Publication Date(Web):
DOI:10.1002/ange.201108220
Co-reporter:Guang-Ning Liu ; Xiao-Ming Jiang ; Mei-Feng Wu ; Guan-E Wang ; Guo-Cong Guo ;Jin-Shun Huang
Inorganic Chemistry 2011 Volume 50(Issue 12) pp:5740-5746
Publication Date(Web):May 20, 2011
DOI:10.1021/ic2005562
A novel one-dimensional (1-D) mixed-valent thioarsenate (III, V), {[Mn(phen)]3(AsVS4)(AsIIIS3)}n·nH2O (1), with a noncentrosymmetric (NCS) polar packing arrangement has been obtained under solvothermal conditions. The noncondensed (AsIIIS3)3– anion in 1 is stabilized by coordinating to [MnII(phen)]2+ complex cations and exhibits an unprecedented μ3-1,2κS:2,3κS′:3κS′′ linkage mode. Compound 1 represents the first example of the stabilization of noncondensed (MQ3)3– (M = As, Sb; Q = S, Se) species only in the coordination of TM(II) complex cations (TM = transition-metal) and the first observation of the coexistence of the (AsVS4)3– tetrahedron and the noncondensed (AsIIIS3)3– pyramid in a single compound. Of particular interest, compound 1 is also an antiferromagnet with TN = 31 K, and exhibits photoluminescence (PL) with a maximum emission at about 438 nm and a second harmonic generation (SHG) response.
Co-reporter:Guang-Ning Liu, Guo-Cong Guo, Ming-Jian Zhang, Jin-Shuang Guo, Hui-Yi Zeng, and Jin-Shun Huang
Inorganic Chemistry 2011 Volume 50(Issue 19) pp:9660-9669
Publication Date(Web):September 8, 2011
DOI:10.1021/ic201413h
1,10-Phenanthroline (phen) and monoprotonated methylamine molecules were used as a novel cotemplate to direct the formation of a new inorganic–organic hybrid selenidostannate, (CH3NH3)4(Sn2Se6)·6phen (1); while the utilization of three types of transition-metal (TM) phen complex cations with the TM/phen ration of 1:1, 1:2, and 1:3 as structure directors affords {[Mn(phen)2]2(μ2-Sn2Se6)}·H2O (2a), {[Fe(phen)2]2(μ2-Sn2Se6)} (2b), {[Mn(phen)]2(μ4-Sn2Se6)}n (3), {[Mn(phen)2](Sn2Se5)}n (4), and [Fe(phen)3]n(Sn3Se7)n·1.25nH2O (5). These compounds show diverse structures with the selenidostannate anions varying from discrete, μ2- and μ4- (Sn2Se6)4– anions, to one-dimensional (1-D) 1∞(Sn2Se52–) anionic chains, and two-dimensional (2-D) extended 2∞(Sn3Se72–) anionic layers, demonstrating different structure-directing abilities of the cotemplate and the three types of TM phen complex cations. This work clearly indicates that the approach of modifying the number of the free coordination sites of unsaturated TM phen complex cations is very exciting as a way to synthesize novel hybrid chalcogenidometalates. Of particular interest, the present compounds exhibit interesting optical properties that reflect the combined effects of both photoluminescence-active organic components and semiconducting inorganic chalcogenidometalate anionic networks.
Co-reporter:Mei-Feng Wu, Ming-Sheng Wang, Sheng-Ping Guo, Fa-Kun Zheng, Hui-Fen Chen, Xiao-Ming Jiang, Guang-Ning Liu, Guo-Cong Guo, and Jin-Shun Huang
Crystal Growth & Design 2011 Volume 11(Issue 2) pp:372-381
Publication Date(Web):January 5, 2011
DOI:10.1021/cg100817s
Reaction of lanthanide oxides and 1H-tetrazolate-5-ethyl formate in water at 50 °C in the presence of pyridine afforded a series of lanthanide coordination polymers, {(Hpy)2[Pr4(tzf)7(H2O)11]·10H2O}n (1) and {[Ln2(tzf)3(H2O)6]·4H2O}n, where Ln = Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Hpy = protonated pyridine, and H2tzf = 1H-tetrazolate-5-formate acid. Polymer 1 features a three-dimensional (3-D) anion framework built up by cross-linkage of tetrameric [Pr4(tzf)4]4+ units and tzf2− ligands, showing a six-connected primitive cubic (pcu) topology (412·63). Isomorphous polymers 2−6 present a two-dimensional (2-D) neutral structure with a four-connected (4,4) topology. Four new coordination modes of the tzf2− ligand are first observed in tetrazolate-5-carboxylate complexes. The lanthanide contraction effect and coordination flexibility of tzf2− ligand play a key role in governing the formation of coordination polymers with different polymeric architectures. The photoluminescent analyses for 2, 3, 5, and 6 suggest that ligand-to-Ln(III) energy transfer is efficient, especially for Eu(III) and Tb(III) ions, and the tzf2− ligand may act as a good “antenna molecule” to sensitize Ln(III) emission. The variable-temperature magnetic study shows that magnetic interactions between the Ln(III) ions in 1−6 are mainly ascribed to the antiferromagnetic coupling as well as the depopulation of the Stark levels. The spin−orbit coupling parameters (λ) for Sm(III) in 2 and Eu(III) in 3 are 259(2) and 344(1) cm−1, respectively, based on the free-ion approximation.
Co-reporter:Guang-Ning Liu, Jian-Di Lin, Zhong-Ning Xu, Zhi-Fa Liu, Guo-Cong Guo, and Jin-Shun Huang
Crystal Growth & Design 2011 Volume 11(Issue 8) pp:3318-3322
Publication Date(Web):June 23, 2011
DOI:10.1021/cg2005826
The first homochiral binuclear metal complex cation-containing inorganic–organic hybrid chalcogenidometalates [Ni2(teta)3](Ge4S10)·H2O (1 and 1′; teta = triethylenetetramine) were prepared, which spontaneously separate in enantiomers upon crystallization; a unique water-mediated hybrid supramolecular helix, and the correlation between molecular chirality and absolute helicity are observed in the entantiomers.
Co-reporter:Ying-Bing Lu, Li-Zhen Cai, Jian-Ping Zou, Xi Liu, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2011 vol. 13(Issue 19) pp:5724-5729
Publication Date(Web):11 Jul 2011
DOI:10.1039/C1CE05497J
Two novel halogeno(cyano)argentates(I), [Et4N]3[Ag6(CN)3.39Br5.61] (1) and [Pp4N]3[Ag8(CN)4I7] (2) (Et4N = tetra-ethylammonium, Pp4N = tetra-n-propylammonium), were obtained by the solvothermal reaction of silver(I) cyanide with tetraalkylammonium salts in anhydrous THF. Complex 1 presents a 2-D grid-like sheet built by [Ag6Br5]+ clusters bridged by cyanide groups. Complex 2 is the first example of 3-D halogeno(cyano)argentates(I), and displays a porous framework with fluorite (flu) topology based on [Ag4I4] and an unprecedented [Ag8I6]2+ cluster, respectively, as 4-connected and 8-connected nodes. The optical and luminescent properties of the two complexes have been investigated. On the basis of Time-dependent Density Functional Theory calculations, the emission spectrum of 1 can be assigned as metal-centred (MC) transitions, while the luminescence behavior for 2 is assumed to arise from metal-to-ligand charge-transfer (MLCT) transitions.
Co-reporter:Jian-Ping Zou, Qiang Peng, Sheng-Lian Luo, Xin-Hua Tang, Ai-Qin Zhang, Gui-Sheng Zeng and Guo-Cong Guo
CrystEngComm 2011 vol. 13(Issue 11) pp:3862-3867
Publication Date(Web):14 Apr 2011
DOI:10.1039/C1CE05047H
A novel quaternary mercury and cadmium chalcogenidehalide, (Hg2Cd2S2Br)Br (1), has been prepared by solid-state reaction and structurally characterized by single crystal X-ray diffraction analysis. The structure of 1 is composed of parallel slabs stacking with -ABAB- mode via linearly coordinated Hg atoms to form a 3D cationic network with the channels being occupied by discrete Br anions, in which the slab consists of interlinks of linear (HgS2Br2) tetrahedral chains and (CdS2Br) trigonal chains. The optical properties were investigated in terms of the diffuse reflectance and Fourier transform infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is a semiconductor with an indirect band gap, and that the optical absorption is mainly originated from the charge transitions from Br-4p and S-3p to Cd-5s and Hg-6s states.
Co-reporter:Xiao-Ming Jiang;Zhong-Ning Xu;Zhong-Yan Zhao;Sheng-Ping Guo;Jin-Shun Huang
European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 26) pp:4069-4076
Publication Date(Web):
DOI:10.1002/ejic.201100091
Abstract
Two new indium arsenic(III) oxide halides, In2(As2O5)Cl2 (1) and In4(As2O5)(As3O7)Br3 (2), have been prepared by solid-state reaction. Both of the compounds feature layered structures, in which indium–oxide halide octahedral rings or indium–oxo chains are bridged by indium–oxide halide octahedral dimers or indium–oxo unicapped trigonal prisms, and the interlinkage between the rings or chains is also consolidated by (As2O5)4– anions for 1, or (As2O5)4– and (As3O7)5– anions for 2. Compound 2 is the first compound in which three different indium-ion coordination geometries coexist with the In3+ cations coordinated by O2– and Br– to form [InO6], [InO7], and [InOBr3] units. The diffuse reflectance spectra and band-structure calculations show that they are wide-band-gap semiconductors.
Co-reporter:Guan-E Wang, Ming-Sheng Wang, Xiao-Ming Jiang, Zhi-Fa Liu, Rong-Guang Lin, Li-Zhen Cai, Guo-Cong Guo, Jin-Shun Huang
Inorganic Chemistry Communications 2011 Volume 14(Issue 12) pp:1957-1961
Publication Date(Web):December 2011
DOI:10.1016/j.inoche.2011.09.020
Two inorganic–organic hybrids, (MPDA)2n(Pb3I10)n (MPDA = p-Me3NC6H4NMe3) (1) and (H2EPDA)n(Pb2I6)n·2nH2O (H2EPDA = p-Et2NHC6H4NHEt2) (2), have been solvothermally synthesized using p-phenylenediamine (PDA) as a precursor. Their iodoplumbate ions all show 1-D chain structures, but differ in interlinkage modes of [PbI6] octahedra: the former is both face- and edge-sharing, while the latter is face-sharing. The chain-like structure in 1 was reported only once in the literature. The results of optical absorption spectra and theoretical calculations for compounds PbI2 and 1–2 reveal a quantum confinement effect. Photoluminescent analyses show that they all exhibit blue emissions upon UV irradiation, which mainly originate from charge transfer from iodine atoms to ammoniums.Graphical abstractThe interlinkage modes of (PbI6) octahedra in 1-D iodoplumbate anions have been found to develop from edge- to face-sharing along with the increase of steric hindrance and the decrease of the charge density of p-phenylenediamine (PDA) derivatives. Photoluminescence (PL) studies suggest that bulk PbI2 is PL silent but introducing the N-alkylated derivatives of PDA to it can result in the generation of PL emission, which mainly originate from the charge transfer from I atoms to ammoniums.Highlights► Study the effect of modification of the same organic ammonium on crystal structure. ► One of the 1-D chain structure of the iodoplumbates was rarely reported. ► Study the influence of templates on absorption edge and photoluminescence emission.
Co-reporter:Ming-Sheng Wang, Gang Xu, Zhang-Jing Zhang and Guo-Cong Guo
Chemical Communications 2010 vol. 46(Issue 3) pp:361-376
Publication Date(Web):01 Dec 2009
DOI:10.1039/B917890B
The distinct synergetic characteristics between each component in inorganic–organic hybrids offer various possibilities to obtain new “smart”, high performing materials. Growing interest in this field has largely expanded the content of photochromic materials for the purpose of improving existing photochromic materials, fabricating photoresponsive devices, and exploring new families of photochromic materials. In this feature article, we give a brief review of photochromic hybrids of metal halides, metal cyanides, polyoxometalates, and metal chalcogenides as well as photochromic metal–organic complexes.
Co-reporter:Gang Xu, Guo-Cong Guo, Jin-Shuang Guo, Sheng-Ping Guo, Xiao-Ming Jiang, Chen Yang, Ming-Sheng Wang and Zhang-Jing Zhang
Dalton Transactions 2010 vol. 39(Issue 37) pp:8688-8692
Publication Date(Web):18 Aug 2010
DOI:10.1039/C0DT00471E
A photochromic inorganic–organic hybrid based on in situ generated MV2+ cation (MV2+ = methyl viologen = N,N′-dimethyl-4,4′-bipyridinium) has been obtained, in which a vagarious partial photochromic phenomenon together with its photoluminescence modulation properties are reported for the first time in the inorganic–organic hybrids.
Co-reporter:Jian-Ping Zou, Qiang Peng, Zhenhai Wen, Gui-Sheng Zeng, Qiu-Ju Xing and Guo-Cong Guo
Crystal Growth & Design 2010 Volume 10(Issue 6) pp:2613
Publication Date(Web):April 27, 2010
DOI:10.1021/cg100104t
Two novel metal−organic frameworks (MOFs) [Cu3(C7H2NO5)2]n·3nH2O (1) and [CuAg2(C7H3NO5)2]n (2) were obtained by the hydrothermal reaction. Complex 1 exhibits a three-dimensional (3,6)-connected anatase topology with the Schläfli symbol (42.6)2(44.62.88.10), while complex 2 displays a two-dimensional (3,6)-connected TiS2 related net topology with the Schläfli symbol (43)2(46.66.83). The optical studies show that 1 and 2 both have good third-order nonlinear optical and luminescent properties.
Co-reporter:Wen-Tong Chen;A-Qing Wu;Ming-Sheng Wang;Li-Zhen Cai;Jin-Shun Huang
European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 18) pp:2826-2835
Publication Date(Web):
DOI:10.1002/ejic.201000112
Abstract
Three series of fourteen cyano-bridged 2D LnIII–FeIII or LnIII–CoIII complexes, [Ln(dmso)2(H2O)(μ-CN)4Fe(CN)2]n [Ln = Gd (1) and Er (2)], [Ln(dmso)2(H2O)3(μ-CN)3M(CN)3]n [La–Fe (3) and Pr–Co (4)], [Ln(dmf)2(H2O)3(μ-CN)3M(CN)3]n·nH2O [Nd–Fe (5), Gd–Fe (6), Dy–Fe (7), Er–Fe (8), Nd–Co (9), and Gd–Co (10)], [Ln(dmso)2(H2O)3(μ-CN)3Co(CN)3]n·nH2O [Ln = Pr (11), Nd (12), and Sm (13)], and [Er(dmf)(H2O)3(μ-CN)4Co(CN)2]n·nH2O (14) (dmso = dimethyl sulfoxide; dmf = N,N′-dimethylformamide) were rationally prepared by the ball-milling method, and their structures were characterized. The crystal structures of 1 and 2 reveal a sevenfold coordination environment of the Ln3+ ions and a 2D stair-like structure, while those of 3–13 show an eightfold coordination environment of the Ln3+ ions and a 2D monolayered brick-wall-like topology and that of 14 exhibits an eightfold coordination environment of the Er3+ ions and a 2D bilayered topology. The relationship between the crystal structures and the controllable synthesis was also discussed.
Co-reporter:Guang-Ning Liu, Guo-Cong Guo, Ming-Sheng Wang, Li-Zhen Cai, Jin-Shun Huang
Journal of Molecular Structure 2010 Volume 983(1–3) pp:104-111
Publication Date(Web):1 November 2010
DOI:10.1016/j.molstruc.2010.08.039
Five new thiogermanates, [NiII(dien)2]2(Ge2S6) (dien = diethylenetriamine) (1), [NiII(dien)2](H2pipe)(Ge2S6) (pipe = piperazine) (2), {[MnII(tren)]2(μ2-Ge2S6)} (tren = N,N,N-tris(2-aminoethyl)amine) (3) and {[MII(tepa)]2(μ2-Ge2S6)} (M = Mn (4a), Ni (4b); tepa = tetraethylenepentamine), have been obtained solvothermally in the presence of tri-(L3), tetra-(L4) and penta-dentate (L5) chelating amines and transition metal (TM) ions. Single-crystal X-ray diffraction analyses show that compounds 1–2 are comprised of discrete (Ge2S6)4− anions and TM complex (TMC) cations, while compounds 3–4b are composed of each dimeric (Ge2S6)4− anion bridging two TMC cations via TM–S bonds to form a neutral molecule. Notably, two interesting in situ metal/ligand reactions were observed in the solvothermal syntheses of 2 and 3. The present compounds exhibit wide optical gap ranging from 2.94 to 3.39 eV and photoluminescence with the emission maxima occurring around 440 (1, 2, 3 and 4b) and 489 nm (4a). Magnetic measurements show the presence of weak antiferromagnetic interactions between magnetic centers in the five compounds.
Co-reporter:Ming-Sheng Wang ; Sheng-Ping Guo ; Yan Li ; Li-Zhen Cai ; Jian-Ping Zou ; Gang Xu ; Wei-Wei Zhou ; Fa-Kun Zheng
Journal of the American Chemical Society 2009 Volume 131(Issue 38) pp:13572-13573
Publication Date(Web):September 2, 2009
DOI:10.1021/ja903947b
A direct white-light metal−organic framework (MOF), [AgL]n·nH2O (1, L = 4-cyanobenzoate), obtained by the reaction of deprotonated 4-cyanobenzoic acid and AgNO3 in water, was found to exhibit tunable yellow-to-white photoluminescence by variation of excitation light. Interestingly, the close pure white emission of 1 has CIE-1931 chromaticity coordinates of (0.33, 0.34) when excited by 349-nm UV light, which is compatible to the light output of the deep UV LED.
Co-reporter:Sheng-Ping Guo, Guo-Cong Guo, Ming-Sheng Wang, Jian-Ping Zou, Hui-Yi Zeng, Li-Zhen Cai and Jin-Shun Huang
Chemical Communications 2009 (Issue 29) pp:4366-4368
Publication Date(Web):19 Jun 2009
DOI:10.1039/B906124J
A novel chiral open-framework structural hexanary chalcogenoborate, (K3I)[SmB12(GaS4)3] (1), was obtained by a facile approach using boron as the reducing reagent; it shows weak SHG-activity and is transparent in the mid-IR region.
Co-reporter:Sheng-Ping Guo, Guo-Cong Guo, Ming-Sheng Wang, Jian-Ping Zou, Gang Xu, Guo-Jian Wang, Xi-Fa Long and Jin-Shun Huang
Inorganic Chemistry 2009 Volume 48(Issue 15) pp:7059-7065
Publication Date(Web):July 9, 2009
DOI:10.1021/ic802443n
Four new quaternary isostructural rare-earth thiosilicates, ZnY6Si2S14 (1), Al0.50Dy3(Si0.50Al0.50)S7 (2), Al0.38Dy3(Si0.85Al0.15)S7 (3), and Al0.33Sm3SiS7 (4), crystallized in the chiral and polar space group P63, have been prepared by a facile synthetic routine. Compounds 1−3 show strong second harmonic generation effects at 2.1 um with the intensities of 1, 2, and 3 being about 2, 2, and 1 times that of KTP (KTiOPO4), respectively. The calculated band structure of 1 implies that the optical absorptions of BLn6M2Q14 and ALn3MQ7 family compounds are mainly ascribed to the charge transitions from Q−p to Ln−4f (4d for Y) states. Compounds 2−4 exhibit antiferromagnetic-like interactions.
Co-reporter:Xi Liu, Kun-Lin Huang, Guo-Ming Liang, Ming-Sheng Wang and Guo-Cong Guo
CrystEngComm 2009 vol. 11(Issue 8) pp:1615-1620
Publication Date(Web):20 Apr 2009
DOI:10.1039/B902121C
Using cyanide anions and sulfur simple substance as precursors of thiocyanate groups, three desired luminescent halogeno-thiocyano-d10 metal complexes, namely, [Me4N][Cu(SCN)Br] (1) with a 1-D to 2-D architecture constructed through C–H⋯Br hydrogen bonds, [Me4N][Cu(SCN)I] (2) with a 1-D to 3-D framework constructed through C–H⋯I hydrogen bonds, and [Me4N][Ag2(SCN)2Cl] (3) with a special 3-D nanoporous structure constructed by µ-chloride atoms connecting the 2-D neutral ∞2[Ag2(SCN)2] layers, have been solvothermally synthesized and all exhibit efficient luminescence. The luminescent behavior of the three complexes was illustrated through the density functional theory.
Co-reporter:Jian-Ping Zou, Guo-Wei Zhou, Xing Zhang, Ming-Sheng Wang, Ying-Bing Lu, Wei-Wei Zhou, Zhang-Jing Zhang, Guo-Cong Guo and Jin-Shun Huang
CrystEngComm 2009 vol. 11(Issue 6) pp:972-974
Publication Date(Web):07 Feb 2009
DOI:10.1039/B900727J
A novel 2-D heterometal-organic coordination polymer [AgCu2(C7H2NO5)(C7H3NO5)]n·2nH2O, obtained by a hydrothermal reaction, exhibits a (44) topology and good third-order nonlinear optical and magnetic properties, which may be a good candidate for NLO and magnetic multifunctional materials.
Co-reporter:Hui-Fen Chen, Guo-Cong Guo, Ming-Sheng Wang, Gang Xu, Wen-Qiang Zou, Sheng-Ping Guo, Mei-Feng Wu and Jin-Shun Huang
Dalton Transactions 2009 (Issue 46) pp:10166-10168
Publication Date(Web):22 Sep 2009
DOI:10.1039/B917559H
The first eight-coordinated trivalent lanthanide complexes with an achiral ligand 6,7-dicyanodipyridoquinoxaline (dicnq), [DyCl3(dicnq)2]n (1 and 1′) were found to exhibit spontaneous chiral resolution, SHG active (two times that of KDP) and blue luminescence.
Co-reporter:Jian-Ping Zou, Sheng-Ping Guo, Xiao-Ming Jiang, Guang-Ning Liu, Guo-Cong Guo, Jin-Shun Huang
Solid State Sciences 2009 Volume 11(Issue 9) pp:1717-1721
Publication Date(Web):September 2009
DOI:10.1016/j.solidstatesciences.2009.05.021
A new supramolecular complex [Hg6Sb4](InBr6)Br (1) has been prepared by the solid-state reaction of HgBr2 with elemental In and Sb at 450 °C. The crystal structure of 1 features a three-dimensional [Hg6Sb4]4+ framework with cavities of two different sizes occupied by different kinds of guest anions. The bigger cavities are filled with the octahedral InBr63− ions, while the smaller cavities trap Br− ions. The optical properties were investigated in terms of the diffuse reflectance and infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is semiconductor, and the optical absorption is mainly originated from the charge transitions from Sb-5p and Br-4p to In-5s and Hg-6s states.
Co-reporter:Jian-Ping Zou, Gui-Sheng Zeng, Zhen-Hai Wen, Qiang Peng, Qiu-Ju Xing, Mei-Hong Chen, Guo-Cong Guo, Jin-Shun Huang
Inorganica Chimica Acta 2009 Volume 362(Issue 13) pp:4843-4848
Publication Date(Web):15 October 2009
DOI:10.1016/j.ica.2009.06.040
A 1D coordination polymer, {[Cu3(C7H2NO5)2(H2O)7]·2(H2O)}n (1), has been synthesized and characterized by X-ray single-crystal diffraction. The crystal structure of 1 features that distorted square–pyramidal coordination polyhedra composed of Cu atoms and chelidamic acid ligands are interlinked into a 1D polymer, further linked by hydrogen bonds into a 3D network. The optical properties were investigated in terms of diffuse reflectance and fluorescent spectra, which exhibit strong luminescence. The electronic band structure along with the density of states (DOSs) calculated by the DFT method indicate that compound 1 pose an energy band gap of 1.89 eV and that the origin of the emission band may be mainly ascribed to metal-to-ligand charge transfer (MLCT) where the electrons are transferred from the Cu-3d to O-2p and C-2p states.A 1D coordination polymer, {[Cu3(C7H2NO5)2(H2O)7]·2(H2O)}n (1), has been synthesized and characterized by X-ray single-crystal diffraction. The crystal structure of 1 features that distorted square–pyramidal coordination polyhedra composed of Cu atoms and chelidamic acid ligands are interlinked into a 1D polymer, further linked by hydrogen bonds into a 3D network.
Co-reporter:Jian-Ping Zou, Qiang Peng, Gui-Sheng Zeng, Zhen-Hai Wen, Qiu-Ju Xing, Mei-Hong Chen, Guo-Cong Guo, Jin-Shun Huang
Journal of Molecular Structure 2009 Volume 921(1–3) pp:323-327
Publication Date(Web):17 March 2009
DOI:10.1016/j.molstruc.2009.01.016
The reaction of Zn(II) ions and chelidamic acid (2,6-dicarboxy-4-hydroxypyridine) gave a novel 1D coordination polymer, [Zn3(C7H2NO5)2·8(H2O)]n (1), which are characterized by X-ray single crystal diffraction. The crystal structure of 1 reveals that Zn(II) centers are linked via chelidamic acid to form one-dimensional chains, further linked by hydrogen bonds to form a 3-D network. The optical properties were investigated in terms of diffuse reflectance and fluorescent spectra, which exhibit strong green luminescence. The electronic band structure along with the density of states (DOS) calculated by the DFT method indicate that compound 1 is a semiconductor and that the origin of the emission band may be mainly ascribed to ligand-to-ligand charge transfer (LLCT) where the electrons are transferred from the O-2p to C-2p states.
Co-reporter:ShengPing Guo;GuoCong Guo;JinShun Huang
Science China Chemistry 2009 Volume 52( Issue 10) pp:1609-1615
Publication Date(Web):2009 October
DOI:10.1007/s11426-009-0238-1
Five new quaternary isostructural rare-earth sulfides, Al0.57Gd3(Si0.27Al0.73)S7 (1), Al0.55Dy3(Si0.34Al0.66)S7 (2), Al0.50Y3(Si0.50Al0.50)S7 (3), Al0.44Gd3(Si0.70Al0.30)S7 (4) and In0.33Sm3SiS7 (5), have been synthesized by facile solid-state reactions. They crystallize in the 3-D ALn3EQ7 structure type in the hexagonal chiral space group P63. The structures feature a 3-D host framework constructed by Ln-S bicapped trigonal prisms, in which the octahedral and tetrahedral interspaces are occupied by A and E atoms, respectively. The investigation of optical and magnetic properties of 4 indicates that it is a semiconductor and behaves antiferromagnetic-like interaction.
Co-reporter:Wei-Wei Zhou, Jiu-Tong Chen, Gang Xu, Ming-Sheng Wang, Jian-Ping Zou, Xi-Fa Long, Guo-Jian Wang, Guo-Cong Guo and Jin-Shun Huang
Chemical Communications 2008 (Issue 24) pp:2762-2764
Publication Date(Web):10 Apr 2008
DOI:10.1039/B801529E
A novel 3-D (3,6)-connected topological architecture, obtained by reacting Cd(ClO4)2·6H2O with Htrtr (Htrtr = 3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole) under solvothermal conditions, presents a non-centrosymmetric polar packing arrangement, resulting in a strong second harmonic generation (SHG) response and ferroelectric property.
Co-reporter:Ying-Bing Lu ; Ming-Sheng Wang ; Wei-Wei Zhou ; Gang Xu ; Guo-Cong Guo ;Jin-Shun Huang
Inorganic Chemistry 2008 Volume 47(Issue 19) pp:8935-8942
Publication Date(Web):September 12, 2008
DOI:10.1021/ic801026y
Two novel manganese(II) tetrazolate coordination polymers, Mn3(Hbta)4(μ2-OH)2(H2O)·2H2O (1) and Mn(bta)(H2O) (2), were obtained by the hydrothermal reaction of MnCl2·4H2O with N,N-bis[1(2)H-tetrazol-5-yl]amine (H2bta) in different pH values. Compound 1 exhibits a 2-D (4,4) layer structure, which is built from binuclear Mn2(μ2-OH)2 subunits and μ3-bridging Hbta− linkers. Compound 2 is a helical framework, and its 3-D PtS-like net is constructed by Mn2(bta)2 dimers and μ5-bridging bta2− linkers. Magnetic measurements reveal that compound 1 displays an antiferromagnetic ordering, while compound 2 exhibits the coexistence of a spin-canted antiferromagnetic coupling and a field-induced spin-flop transition.
Co-reporter:Yan Li ; Gang Xu ; Wen-Qiang Zou ; Ming-Sheng Wang ; Fa-Kun Zheng ; Mei-Feng Wu ; Hui-Yi Zeng ; Guo-Cong Guo ;Jin-Shun Huang
Inorganic Chemistry 2008 Volume 47(Issue 18) pp:7945-7947
Publication Date(Web):August 9, 2008
DOI:10.1021/ic800761h
A novel zinc(II) 4-(5H-tetrazol)benzoic coordination polymer with an in situ generated tetrazole ligand exhibits the gsi (γ-silicon) topology and high thermal stability; this compound possesses second-order nonlinear optical and interesting heat-induced photoluminescent properties.
Co-reporter:Jian-Ping Zou, Ming-Sheng Wang, Ke-Jun Wu, Guo-Cong Guo, Yan Li, Zhang-Jing Zhang, Jin-Shun Huang
Solid State Sciences 2008 Volume 10(Issue 1) pp:69-73
Publication Date(Web):January 2008
DOI:10.1016/j.solidstatesciences.2007.08.004
A new synthetic approach with the advantage of low cost and facile operation, which is characterized by using Hg(CN)2 as starting material, has been successfully established for the preparation of Hg1−XCdxTe (MCT) materials with different x values, especially the Hg rich MCT. Three new compounds, namely Hg0.90Cd0.10Te (1), Hg0.32Cd0.68Te (2) and Hg0.29Cd0.71Te (3), have been synthesized, respectively. These compounds possess sphalerite structures with the space group F-43m. Their optical properties were investigated in terms of the diffuse reflectance and Fourier transform infrared spectra. Electronic band structures along with density of states (DOS) calculated by DFT method indicate that the present compounds belong to direct semiconductors and their optical absorptions are mainly originated from the charge transitions from Te-5p to Cd-5s and Hg-6s states.
Co-reporter:Tong-Yong Ding, Ming-Sheng Wang, Sheng-Ping Guo, Guo-Cong Guo, Jin-Shun Huang
Materials Letters 2008 Volume 62(Issue 30) pp:4529-4531
Publication Date(Web):15 December 2008
DOI:10.1016/j.matlet.2008.08.031
CuS nanoflowers with a specific surface area of 18.8 m2/g were prepared through a rapid polyol route at 140 °C for 90 min, and characterized by XRD, SEM, UV–vis spectrum and BET surface area. The formation of CuS nanoflowers is proposed to experience an aggregation and growth process. The photocatalytic activity of CuS nanoflowers was investigated by decomposing Rhodamine B at atmosphere and the result shows that the photocatalytic activity under halogen lamp irradiation is comparable to that of Degussa P25 TiO2.
Co-reporter:Ming-Sheng Wang Dr., Dr.;Wen-Qiang Zou;Wei-Wei Zhou;Zhang-Jing Zhang Dr.;Gang Xu ;Jin-Shun Huang
Angewandte Chemie 2008 Volume 120( Issue 19) pp:3621-3623
Publication Date(Web):
DOI:10.1002/ange.200705545
Co-reporter:Zhang-Jing Zhang;Sheng-Chang Xiang, ;Gang Xu;Ming-Sheng Wang;Jian-Ping Zou;Sheng-Ping Guo ;Jing-Shun Huang
Angewandte Chemie 2008 Volume 120( Issue 22) pp:4217-4220
Publication Date(Web):
DOI:10.1002/ange.200800603
Co-reporter:Ming-Sheng Wang Dr., Dr.;Wen-Qiang Zou;Wei-Wei Zhou;Zhang-Jing Zhang Dr.;Gang Xu ;Jin-Shun Huang
Angewandte Chemie International Edition 2008 Volume 47( Issue 19) pp:3565-3567
Publication Date(Web):
DOI:10.1002/anie.200705545
Co-reporter:Zhang-Jing Zhang;Sheng-Chang Xiang, ;Gang Xu;Ming-Sheng Wang;Jian-Ping Zou;Sheng-Ping Guo ;Jing-Shun Huang
Angewandte Chemie International Edition 2008 Volume 47( Issue 22) pp:4149-4152
Publication Date(Web):
DOI:10.1002/anie.200800603
Co-reporter:Ming-Lai Fu, Guo-Cong Guo, Xi Liu, Jian-Ping Zou, Gang Xu and Jin-Shun Huang
Crystal Growth & Design 2007 Volume 7(Issue 12) pp:2387
Publication Date(Web):November 3, 2007
DOI:10.1021/cg070637v
A novel manganese polysulfido hybrid, [Mn(2,2′-bipy)2S6]n, which is the first example with Qn2– (Q = S, Se, Te, n ≥ 1) as a bridging ligand connecting metal atoms to form a one-dimensional helical chain, has been synthesized and structurally characterized. The compound exhibits semiconducting properties (Eg = 1.67 eV) and strong blue photoluminescence with the emission maximum occurring around 400 nm, and the variable-temperature magnetic susceptibility data suggest a weak antiferromagnetic interaction among Mn2+ ions in the compound.
Co-reporter:Jian-Ping Zou, Guo-Cong Guo, Sheng-Ping Guo, Ying-Bing Lu, Ke-Jun Wu, Ming-Sheng Wang and Jin-Shun Huang
Dalton Transactions 2007 (Issue 42) pp:4854-4858
Publication Date(Web):28 Aug 2007
DOI:10.1039/B706844A
A new mixed-framework mercury selenide diselenite, (Hg3Se2)(Se2O5) (1), has been prepared by a solid-state reaction and structurally characterized by single-crystal X-ray diffraction analysis. The crystal structure of 1 consists of parallel stair-like cationic (Hg3Se2)2+ chains, which are bridged by (Se2O5)2− anionic groups to form a novel 2-D layered mixed-framework. The optical properties were investigated in terms of the diffuse reflectance and microscopic infrared spectra. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 is a semiconductor, and that the optical absorption of 1 is mainly ascribed to the charge transitions from the O-2p and Se(−II)-4p states to the Se(IV)-4p and Hg-6s states.
Co-reporter:Hui-Yi Zeng, Fa-Kun Zheng, Rui-Ping Chen, Zhen-Chao Dong, Guo-Cong Guo, Jin-Shun Huang
Journal of Alloys and Compounds 2007 Volume 432(1–2) pp:69-73
Publication Date(Web):25 April 2007
DOI:10.1016/j.jallcom.2006.06.010
High-quality single crystals of RbInS2, CsInS2 were isolated from the halide flux as a major phase of the repeated fusion of CaS and In2S3 followed by slow cooling. RbInS2 and CsInS2 are practically isostructural with KInS2. RbInS2: C2/c, a = 11.071(6) Å, b = 11.068(1) Å, c = 15.610(7) Å, β = 100.36(3)°, V = 1882(2) Å3, Z = 16, dx = 3.74 g/cm3, R = 6.38%, Rw = 6.42%. CsInS2: C2/c, a = 11.197(3) Å, b = 11.158(3) Å, c = 16.358(4) Å, β = 99.92(2)°, V = 2013(2) Å3, Z = 16, dx = 4.12 g/cm3, R = 5.60%, Rw = 6.20%. The AInS2 (A = Rb, Cs) structure is characterized by double layers of vertex-sharing [In4S10] units that each consists of four [InS4] polyhedra. The charge-balancing alkali-metal cations are stuffed into the channels created by the packing of these anionic [In4S10] blocks. The optical reflectance measurements show a band gap of 3.3 eV for RbInS2 and 3.4 eV for CsInS2, suggesting that both are semiconductors.
Co-reporter:Guo-Wei Zhou, You-Zhao Lan, Fa-Kun Zheng, Xin Zhang, Meng-Hai Lin, Guo-Cong Guo, Jin-Shun Huang
Chemical Physics Letters 2006 Volume 426(4–6) pp:341-344
Publication Date(Web):4 August 2006
DOI:10.1016/j.cplett.2006.06.034
Abstract
[Zn(C7H3O5N)]n · nH2O (1) possesses an anticlockwise windmill-like framework structure and formats spiroconjugation over the infinite molecular layer that is predicted to have large static third-order polarizability and the convergence value of γxxxx reaches 6.86 × 10−33 esu in the case of zero input photon energy. The third-order NLO properties of 1 were investigated via Z-scan techniques at wavelength of 532 nm. It showed strong third-order NLO absorptive properties, and its n2 value was calculated to be 4.15 × 10−11 esu. The relationship between the spiroconjugated structure and the NLO property has been discussed, which supposed to be more valuable for the NLO research.
Co-reporter:Li-Zhen Cai, Guo-Cong Guo, Ming-Lai Fu, Ming-Sheng Wang, Wen-Tong Chen, Jin-Shun Huang
Inorganica Chimica Acta 2006 Volume 359(Issue 14) pp:4483-4492
Publication Date(Web):1 November 2006
DOI:10.1016/j.ica.2006.05.039
Assembly of isonicotinic acid ligand (HL) with metal halide, five new hybrid complexes [CdI2(C5H4NCOOH)(C5H4NHCOO)] · H2O (1), Nan[ZnCl2(C5H4NCOO)]n · 2nH2O (2), [CdX(C5H4NCOO)]n (X = Br (3), I (4)) and [Cd3Cl2(OH)2(C5H4NCOO)2]n (5) were obtained, which display a variety of structural motifs, ranging from zero-dimensional to complicated three-dimensional networks. Complex 1 possesses an isolated unit MX2 that is further connected into 3D networks through hydrogen bonding and π–π stacking interactions. Complex 2 is characterized by an infinite one-dimensional chain of zinc atoms bridged by L− ligands. While complexes 3 and 4 possess X-bridging ∞1[CdX2/2]∞1[CdX2/2] inorganic chains connected by L− ligands to form a 2D hybrid network structure. In the case of 5, the cadmium(II) cation is bridged by μ3-Cl atom and μ3-OH− group to form a 2-D ∞2[Cd6/2Cl6/3(μ3-OH)2]∞2[Cd6/2Cl6/3(μ3-OH)2] inorganic layer which is further extended into 3-D framework by bridging L− ligand via Cd–N and Cd–O bonds. The optical properties of 1, 4, and 5 in the solid state are investigated at room temperature and time-dependent DFT (TDDFT) calculation using the B3LYP functional has been performed on 1. The result indicated that the emission band of 1 is attributed to an admixture of MLCT (metal-to-ligand charge–transfer) and LLCT (ligand-to-ligand charge-transfer).Five new inorganic–organic hybrids composed of group 12 metal halide and isonicotinic ligand have been synthesized and optical properties for some complexes have been studied. The structure diversities of the present compounds are influenced by the coordination numbers of M2+ and the bridging modes of X− ions and HL ligand.
Co-reporter:Ru-Qiang Zou, Li-Zhen Cai, Guo-Cong Guo
Journal of Molecular Structure 2005 Volume 737(2–3) pp:125-129
Publication Date(Web):4 March 2005
DOI:10.1016/j.molstruc.2004.10.014
A six-coordinated monomeric CoII complex, [Co(L)2(H2O)4]·10H2O (1), where HL=4-(p-benzoxy)-1,2,4-triazole, has been synthesized and characterized by elemental analyses, IR, thermogravimetric analysis and X-ray diffraction technique. Structural analyses reveal that the CoII center has a CoN2O4 octahedral environment with four O atoms of coordinated water molecules constituting the equatorial plane and two N atoms of two distinct L ligands occupying the two axial sites in 1. A striking structural feature of 1 resides in the formation of a three-dimensional (3D) supramolecular architecture through intermolecular O–H⋯O hydrogen-bonding interactions. Complex 1 displays strong blue emission in the solid state.
Co-reporter:Sheng-Ping Guo, Yang Chi, Guo-Cong Guo
Coordination Chemistry Reviews (15 March 2017) Volume 335() pp:
Publication Date(Web):15 March 2017
DOI:10.1016/j.ccr.2016.12.013
•Recent achievements on three main types of middle and far-infrared NLO materials are reviewed.•Materials with double types of anion are promising.•Alkali-metal and Ba chalcogenides are studied extensively.•Functional moiety theory is employed to help exploration of NLO materials.The exploration and development of second-order nonlinear optical (NLO) materials in the middle- and far infrared (MFIR) region are important and high profile topics in the fields of NLO, solid-state chemistry and laser. Common MFIR NLO materials are chalcogenides, halides, and iodates, which have a wide MFIR transparent range and large NLO coefficients. This review summarizes recent achievements on MFIR NLO materials, and specifically focuses on their crystal structures and NLO properties. Compared to known materials, the common choice for cations are alkali-metal Li, Na, K, Rb and Cs, the coin-metal Ag, and the alkali-earth metal Ba. Exploring mixed-anions materials could be one of the most promising solutions to obtaining NLO materials with both large second-harmonic generation (SHG) intensities and high laser induced damage thresholds (LIDTs). This review also summarizes functional moiety theory to elucidate the design of promising NLO materials.
Co-reporter:Xian Zhang, Ming-Sheng Wang, Cai Sun, Chen Yang, Pei-Xin Li and Guo-Cong Guo
Chemical Communications 2016 - vol. 52(Issue 51) pp:NaN7949-7949
Publication Date(Web):2016/05/23
DOI:10.1039/C6CC03354G
With the help of theoretical predictions, we have found, from the [donor–metal–acceptor] system, the first photochromic pyrazine-based compound that can undergo photoinduced charge separation and yield stable pyrazine radicals.
Co-reporter:Si-Yan Peng, Zhong-Ning Xu, Qing-Song Chen, Yu-Min Chen, Jing Sun, Zhi-Qiao Wang, Ming-Sheng Wang and Guo-Cong Guo
Chemical Communications 2013 - vol. 49(Issue 51) pp:NaN5720-5720
Publication Date(Web):2013/03/22
DOI:10.1039/C3CC00219E
A Pd/α-Al2O3 nanocatalyst with ultra-low Pd loading exhibits high activity and stability for CO oxidative coupling to dimethyl oxalate, which was prepared by a Cu2+-assisted in situ reduction method at room temperature. The small size and high dispersion of Pd nanoparticles facilitated by Cu2+ ions are responsible for the excellent catalytic activity.
Co-reporter:Sheng-Ping Guo, Guo-Cong Guo, Ming-Sheng Wang, Jian-Ping Zou, Hui-Yi Zeng, Li-Zhen Cai and Jin-Shun Huang
Chemical Communications 2009(Issue 29) pp:NaN4368-4368
Publication Date(Web):2009/06/19
DOI:10.1039/B906124J
A novel chiral open-framework structural hexanary chalcogenoborate, (K3I)[SmB12(GaS4)3] (1), was obtained by a facile approach using boron as the reducing reagent; it shows weak SHG-activity and is transparent in the mid-IR region.
Co-reporter:Wei-Wei Zhou, Jiu-Tong Chen, Gang Xu, Ming-Sheng Wang, Jian-Ping Zou, Xi-Fa Long, Guo-Jian Wang, Guo-Cong Guo and Jin-Shun Huang
Chemical Communications 2008(Issue 24) pp:NaN2764-2764
Publication Date(Web):2008/04/10
DOI:10.1039/B801529E
A novel 3-D (3,6)-connected topological architecture, obtained by reacting Cd(ClO4)2·6H2O with Htrtr (Htrtr = 3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole) under solvothermal conditions, presents a non-centrosymmetric polar packing arrangement, resulting in a strong second harmonic generation (SHG) response and ferroelectric property.
Co-reporter:Guan-E Wang, Gang Xu, Ming-Sheng Wang, Li-Zhen Cai, Wen-Hua Li and Guo-Cong Guo
Chemical Science (2010-Present) 2015 - vol. 6(Issue 12) pp:NaN7226-7226
Publication Date(Web):2015/09/17
DOI:10.1039/C5SC02501J
Single-component white light materials may create great opportunities for novel conventional lighting applications and display systems; however, their reported color rendering index (CRI) values, one of the key parameters for lighting, are less than 90, which does not satisfy the demand of color-critical upmarket applications, such as photography, cinematography, and art galleries. In this work, two semiconductive chloroplumbate (chloride anion of lead(II)) hybrids, obtained using a new inorganic–organic hybrid strategy, show unprecedented 3-D inorganic framework structures and white-light-emitting properties with high CRI values around 90, one of which shows the highest value to date.
Co-reporter:Sheng-Ping Guo, Yang Chi, Bin-Wen Liu and Guo-Cong Guo
Dalton Transactions 2016 - vol. 45(Issue 25) pp:NaN10465-10465
Publication Date(Web):2016/05/16
DOI:10.1039/C6DT01602B
A novel pentanary selenide (K3I)[InB12(InSe4)3] was obtained via a high-temperature solid-state method. It crystallizes in the hexagonal space group P6322 which features an InSe4 tetrahedron consolidated B12 icosahedron and 1-D chain constructed by InSe6 octahedron and B12Se12 cluster alternatively connected along the c-axis. Second-order nonlinear optical property measurement shows that it is second harmonic generation-active. Theory calculation indicates that it is an indirect semiconductor with the energy gap of 1.15 eV.
Co-reporter:Guan-E Wang, Gang Xu, Ming-Sheng Wang, Jing Sun, Zhong-Ning Xu, Guo-Cong Guo and Jin-Shun Huang
Journal of Materials Chemistry A 2012 - vol. 22(Issue 33) pp:
Publication Date(Web):
DOI:10.1039/C2JM32830E
Co-reporter:Ming-Jian Zhang, Xiao-Ming Jiang, Liu-Jiang Zhou and Guo-Cong Guo
Journal of Materials Chemistry A 2013 - vol. 1(Issue 31) pp:NaN4760-4760
Publication Date(Web):2013/06/04
DOI:10.1039/C3TC30808A
Two phases of Ga2S3 with different space groups Cc and F3m were synthesized in pure phase by a facile boron–sulfur–metallic oxide reaction. They both have a good transparency in the wavelength range of 0.44–25 μm and exhibit comparatively large second-harmonic generation (SHG) effects of about 0.7 and 0.5 times that of commercial KTiOPO4 (KTP), for the monoclinic and cubic Ga2S3 respectively. The monoclinic Ga2S3 is phase-matchable at the wavelength of 1910 nm while the cubic phase is non-phase-matchable. In order to study their powder laser induced damage threshold (LIDT) properties, a single pulse powder LIDT measurement method was proposed and it was found that they have very high powder LIDTs of about 30 and 100 times that of AgGaS2 (AGS), respectively for the monoclinic and cubic phase, under a single pulse 1064 nm laser radiation with a pulse width τp of 8 ns. To gain further insights into the nonlinear optical (NLO) and LIDT properties of the monoclinic and cubic Ga2S3, calculations of second-order NLO susceptibility and lattice energy density (LED) were also performed to explain their SHG efficiencies and high LIDTs.
Co-reporter:Pei-Xin Li, Ming-Sheng Wang, Li-Zhen Cai, Guan-E. Wang and Guo-Cong Guo
Journal of Materials Chemistry A 2015 - vol. 3(Issue 2) pp:NaN256-256
Publication Date(Web):2014/11/17
DOI:10.1039/C4TC01315H
Two new isostructural coordination compounds exhibit the rare difunctional properties of both electron-transfer (ET) photochromism and ET thermochromism, which are significantly affected by halogen atoms. The thermocrystallographic studies of the same single crystal have elucidated the electron-donating nature of the halogen atoms.
Co-reporter:Sheng-Ping Guo and Guo-Cong Guo
Journal of Materials Chemistry A 2014 - vol. 2(Issue 48) pp:NaN20628-20628
Publication Date(Web):2014/10/17
DOI:10.1039/C4TA04757E
The ternary dysprosium sulfur telluride Dy4S4Te3 was synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the monoclinic space group C2/m with a = 6.720 (1), b = 13.748 (2), c = 6.715 (1) Å and β = 103.36 (1)°, belongs to the Ho4S4Te2.68 structure type, and its 3-D structure features 2-D ladder-like (DyS)n layers linked by Dy–Te1 and Dy–Te2 bonds with additional Te1–Te1 dumbbells. The (DyS)n layers and the (DyQ)n (Q = S, Se and Te) layers in other binary Dy–Q compounds are compared. Measurement of it magnetic susceptibility shows its paramagnetic behavior. The investigation of its optical properties indicates that it has an energy gap of 1.43 eV, which is also verified by the electronic band structure calculation via the Vienna ab initio simulation package (VASP). The photocatalytic behavior of the polycrystalline powder sample investigated by decomposing rhodamine B under halogen lamp irradiation indicates that its photocatalytic activity can be comparable to that of Degussa P25 TiO2.
Co-reporter:Jian-Ping Zou, Guo-Cong Guo, Sheng-Ping Guo, Ying-Bing Lu, Ke-Jun Wu, Ming-Sheng Wang and Jin-Shun Huang
Dalton Transactions 2007(Issue 42) pp:NaN4858-4858
Publication Date(Web):2007/08/28
DOI:10.1039/B706844A
A new mixed-framework mercury selenide diselenite, (Hg3Se2)(Se2O5) (1), has been prepared by a solid-state reaction and structurally characterized by single-crystal X-ray diffraction analysis. The crystal structure of 1 consists of parallel stair-like cationic (Hg3Se2)2+ chains, which are bridged by (Se2O5)2− anionic groups to form a novel 2-D layered mixed-framework. The optical properties were investigated in terms of the diffuse reflectance and microscopic infrared spectra. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 is a semiconductor, and that the optical absorption of 1 is mainly ascribed to the charge transitions from the O-2p and Se(−II)-4p states to the Se(IV)-4p and Hg-6s states.
Co-reporter:Hui-Fen Chen, Guo-Cong Guo, Ming-Sheng Wang, Gang Xu, Wen-Qiang Zou, Sheng-Ping Guo, Mei-Feng Wu and Jin-Shun Huang
Dalton Transactions 2009(Issue 46) pp:NaN10168-10168
Publication Date(Web):2009/09/22
DOI:10.1039/B917559H
The first eight-coordinated trivalent lanthanide complexes with an achiral ligand 6,7-dicyanodipyridoquinoxaline (dicnq), [DyCl3(dicnq)2]n (1 and 1′) were found to exhibit spontaneous chiral resolution, SHG active (two times that of KDP) and blue luminescence.
Co-reporter:Gang Xu, Guo-Cong Guo, Jin-Shuang Guo, Sheng-Ping Guo, Xiao-Ming Jiang, Chen Yang, Ming-Sheng Wang and Zhang-Jing Zhang
Dalton Transactions 2010 - vol. 39(Issue 37) pp:NaN8692-8692
Publication Date(Web):2010/08/18
DOI:10.1039/C0DT00471E
A photochromic inorganic–organic hybrid based on in situ generated MV2+ cation (MV2+ = methyl viologen = N,N′-dimethyl-4,4′-bipyridinium) has been obtained, in which a vagarious partial photochromic phenomenon together with its photoluminescence modulation properties are reported for the first time in the inorganic–organic hybrids.
Co-reporter:Xiao-Ming Jiang, Xiao-Guo Li, Yu-Hang Fan, Bin-Wen Liu, Hui-Yi Zeng and Guo-Cong Guo
Dalton Transactions 2013 - vol. 42(Issue 43) pp:NaN15481-15481
Publication Date(Web):2013/09/11
DOI:10.1039/C3DT51451J
Two new inorganic supramolecular compounds, (Hg11P4)(GaCl4)4 (1) and (Hg3AsS)(GaCl4) (2), have been prepared by the solid-state reactions. Their structures are characterized by mercury-containing cationic hosts and discrete (GaCl4)− guests, which is a derivative of a very strong Lewis acid. The three-dimensional cationic framework of 1, (Hg11P4)4+, is marvellously extended by Hg22+ and Hg32+ groups as well as Hg2+ ions to form two large tunnels with different sizes each embedded with two columns of (GaCl4)− anions. Compound 2 features a layered structure with (GaCl4)− tetrahedra being intercalated between two-dimensional (Hg3AsS)+ layers and it is the first mercury pnictidechalcohalide. It is found that the weak electrostatic forces between hosts and guests play a key role in the stabilization of the whole structures of 1 and 2, which is strikingly different from almost all the reported metal pnictidehalide and chalcohalide supramolecular compounds. Optical dielectric constants calculations show that both 1 and 2 possess strong dielectric anisotropy.
Co-reporter:Ming-Jian Zhang, Bing-Xuan Li, Bin-Wen Liu, Yu-Hang Fan, Xiao-Guo Li, Hi-Yi Zeng and Guo-Cong Guo
Dalton Transactions 2013 - vol. 42(Issue 39) pp:NaN14229-14229
Publication Date(Web):2013/07/17
DOI:10.1039/C3DT51139A
Two new ternary rare earth chalcogenides, Dy3GaS6 (1) and Y3GaS6 (2), are reported here. They both crystallize in the orthorhombic space group Cmc21 (no. 36). Both are synthesized in pure phase and show phase-matchable second harmonic generation (SHG) of about 0.2 and 0.5 times, respectively for 1 and 2, as strong as that of KTiOPO4 (KTP) based on the powder SHG measurement at the wavelength of 1910 nm. They possess high powder laser induced damage thresholds (LIDTs), respectively, about 14 and 18 times that of AgGaS2 (AGS) based on the powder LIDT measurements under 1064 nm laser irradiation. They both exhibit wide transparency in the IR region (2.5–25 μm). It is believed that the title compounds are new candidates for nonlinear optical (NLO) materials in the IR region. To gain further insights into the NLO and LIDT properties of 1 and 2, the calculations of second-order NLO susceptibility and lattice energy density (LED) were also performed to explain their SHG efficiencies and high LIDTs.
Co-reporter:Guang-Ning Liu, Guo-Cong Guo, Ming-Sheng Wang and Jin-Shun Huang
Dalton Transactions 2014 - vol. 43(Issue 10) pp:NaN3938-3938
Publication Date(Web):2014/01/03
DOI:10.1039/C3DT53515K
Two novel manganese thioarsenates, {[Mn(2,2′-bipy)2(SCN)][Mn(2,2′-bipy)](AsVS4)}2 (1, 2,2′-bipy = 2,2′-bipyridine) and {[Mn(2,2′-bipy)2(SCN)]2[AsIII2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2′-bipy complex cations were synthesized. They feature two terminal [Mn(2,2′-bipy)2(SCN)]+ complex cations bridged by a polyanion {[Mn(2,2′-bipy)]2(AsVS4)2}2− for 1 and a cyclic thioarsenate anion (AsIII2S6)2− for 2. In 2, the [AsIII2(S2)2S2]2− anion can be described as two (AsIIIS3)3− trigonal-pyramids interlinked through S–S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between MnII centers in the two compounds.
Co-reporter:Bin-Wen Liu, Hui-Yi Zeng, Xiao-Ming Jiang, Guan-E Wang, Shu-Fang Li, Li Xu and Guo-Cong Guo
Chemical Science (2010-Present) 2016 - vol. 7(Issue 9) pp:
Publication Date(Web):
DOI:10.1039/C6SC01907B
Co-reporter:Feng Luo, Ming-Sheng Wang, Ming-Biao Luo, Gong-Ming Sun, Yu-Mei Song, Pei-Xin Li and Guo-Cong Guo
Chemical Communications 2012 - vol. 48(Issue 48) pp:NaN5991-5991
Publication Date(Web):2012/04/24
DOI:10.1039/C2CC32103C
This work presents a prototype of chiral porous metal–organic framework with the porous wall decorated by different functional groups. The special structure in conjunction with the gas adsorption results reveals some relationship between CO2 adsorption and functional points. Moreover, outstanding tunable photoluminescence and direct white-light emission is observed.
Co-reporter:Ming-Sheng Wang, Gang Xu, Zhang-Jing Zhang and Guo-Cong Guo
Chemical Communications 2010 - vol. 46(Issue 3) pp:NaN376-376
Publication Date(Web):2009/12/01
DOI:10.1039/B917890B
The distinct synergetic characteristics between each component in inorganic–organic hybrids offer various possibilities to obtain new “smart”, high performing materials. Growing interest in this field has largely expanded the content of photochromic materials for the purpose of improving existing photochromic materials, fabricating photoresponsive devices, and exploring new families of photochromic materials. In this feature article, we give a brief review of photochromic hybrids of metal halides, metal cyanides, polyoxometalates, and metal chalcogenides as well as photochromic metal–organic complexes.
Co-reporter:Yumin Chen, Qing-Song Chen, Si-Yan Peng, Zhi-Qiao Wang, Gang Lu and Guo-Cong Guo
Chemical Communications 2014 - vol. 50(Issue 14) pp:NaN1664-1664
Publication Date(Web):2013/11/21
DOI:10.1039/C3CC47567K
Manipulating the degrees of concavity or Miller indices of high-index facets is significant for metal nanocrystals to further tailor their properties; however, generating a concave surface with negative curvature is still in the early development stage and tuning the degree of concavity remains a challenge. Herein, we have developed a simple and effective site-selective etching strategy to manipulate the concavity of rhodium (Rh) nanocrystals with high-index facets.
Co-reporter:Si-Yan Peng, Zhong-Ning Xu, Qing-Song Chen, Zhi-Qiao Wang, Yumin Chen, Dong-Mei Lv, Gang Lu and Guo-Cong Guo
Catalysis Science & Technology (2011-Present) 2014 - vol. 4(Issue 7) pp:NaN1930-1930
Publication Date(Web):2014/04/16
DOI:10.1039/C4CY00245H
Pd/MgO catalysts are found, for the first time, to be extraordinarily active and stable for CO oxidative coupling to dimethyl oxalate. A series of Pd/MgO catalysts with Pd loadings of 0.1, 0.3, 0.5, 1 and 2 wt% were prepared by a wet impregnation method and systematically characterized by XRD, TEM, ICP, UV-DRS, H2-TPR and CO2-TPD. It has been demonstrated that the amount of Pd loading has a pronounced effect on the catalytic activity for CO oxidative coupling to dimethyl oxalate. CO conversion increases with the increase of the Pd loading due to high dispersion and similar sizes of Pd nanoparticles, as well as, the increase in number of surface active sites.
Co-reporter:Dong-Mei Lv, Zhong-Ning Xu, Si-Yan Peng, Zhi-Qiao Wang, Qing-Song Chen, Yumin Chen and Guo-Cong Guo
Catalysis Science & Technology (2011-Present) 2015 - vol. 5(Issue 6) pp:NaN3339-3339
Publication Date(Web):2015/04/15
DOI:10.1039/C5CY00251F
(Pd–CuCl2)/γ-Al2O3 catalyst with excellent activity and selectivity has been successfully developed for vapor-phase carbonylation of methyl nitrite to dimethyl carbonate (DMC). It has been demonstrated that Cl− is necessary for the superior selectivity (99.8%) to DMC, and that Cl− and Cu2+ have a synergetic effect. The Lewis acid sites of the γ-Al2O3 support may be suitable for vapor-phase carbonylation of methyl nitrite to DMC. Moreover, the catalytic mechanism of DMC formation on the (Pd–CuCl2)/γ-Al2O3 catalyst has been reasonably proposed based on the results of XPS and in situ diffuse reflectance infrared spectroscopy. The intermediate Cl–Pd(II)–COOCH3 is the key factor for the synthesis of DMC.
Co-reporter:Ming-Sheng Wang and Guo-Cong Guo
Chemical Communications 2016 - vol. 52(Issue 90) pp:NaN13204-13204
Publication Date(Web):2016/08/31
DOI:10.1039/C6CC03184F
Light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs) have brought about a revolution in lighting and display. A very hot field in recent years has been to develop white-light phosphors, aiming to achieve better colour stability, better reproducibility, and a simpler fabrication process for LEDs and OLEDs. This feature article reviews the development of inorganic–organic hybrid white-light phosphors, including coordination compounds of small organic molecules, organically templated inorganic compounds (phosphates, borates, sulfides, halides), metal-functionalized organic polymers, and organically coated nanoparticles.
Co-reporter:Sheng-Ping Guo, Guan-E Wang, Ming-Jian Zhang, Mei-Feng Wu, Guang-Ning Liu, Xiao-Ming Jiang, Guo-Cong Guo and Jin-Shun Huang
Dalton Transactions 2013 - vol. 42(Issue 8) pp:NaN2682-2682
Publication Date(Web):2012/12/19
DOI:10.1039/C2DT32321D
A series of rare-earth zirconium chalcogenides Ln2ZrQ5 (Ln = La, Sm, Gd; Q = S, Se) synthesized by using boron as the reducing reagent show unprecedented single-crystal's intrinsic voltage-dependent effects and order antiferromagnetically.
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