Co-reporter:Hui Zheng;Peng Li;Lisheng Gao;Guangming Li
RSC Advances (2011-Present) 2017 vol. 7(Issue 41) pp:25725-25731
Publication Date(Web):2017/05/10
DOI:10.1039/C7RA02354E
Semiconductor-based photocatalysts have been proposed owing to their potential applications in contaminated water remediation, where a silver halide exhibits more attractive performance. Herein, a hexagonal AgBr crystal plate has been synthesized through a facile solvothermal technique, which demonstrated high efficiency for wastewater management through two degradation pathways in the oxidation of methyl orange (MO) and the photo-reduction of hexavalent chromium (CrVI). In order to concretely evaluate the photocatalytic performance, reaction rate constants (κ) of MO and CrVI were calculated to be 0.43 min−1 (>400 nm), 0.73 min−1 (AM 1.5) and 0.01 min−1 (>400 nm), 0.05 min−1 (AM 1.5), which were calculated to be 2.9 and 7.7 times that of the irregular AgBr, respectively. Furthermore, the corresponding mechanisms were also put forward to deeply understand each photocatalytic process.
Co-reporter:Yumei Yue, Guangfeng Hou, Xu Yao, Guangming Li
Polyhedron 2017 Volume 129(Volume 129) pp:
Publication Date(Web):17 June 2017
DOI:10.1016/j.poly.2017.03.040
A series of four new Salen-type lanthanide coordination polymers, e.g. [Ln(H2L)1.5Cl3]n (Ln = Tb (1), Dy (2), Ho (3), and Er (4); H2L = N,N′-bis(salicylidene)-1,4-butanediamine) have been synthesized by self-assembly and characterized by X-ray crystallography. Complexes 1–4 are isomorphic and exhibit one-dimensional alternating single/double ligand-bridge helix-like chain structures in which metal ion is six-coordinated in a slightly distorted octahedral geometry. Detailed magnetic studies suggest that the coordination polymer, especially complex 2, exhibits a typical single-molecule magnet behavior with the energy barrier of 24.4 K.The flexible Salen-type lanthanide coordination polymers represent six-coordinated pure 4f SMMs with the 1D single/double-alternate-ligand-bridged helix-like chain.Download high-res image (178KB)Download full-size image
Co-reporter:Yanping Dong, Weizuo Li, Xiaoyan Zou, Guangfeng Hou, Guangming Li
Inorganica Chimica Acta 2017 Volume 466(Volume 466) pp:
Publication Date(Web):1 September 2017
DOI:10.1016/j.ica.2017.06.019
•A series of three eight-coordinated 5,6-DTFI mononuclear Ln(III) complexes 1–3 were successfully isolated (Ln = Dy, Tb, Ho).•In comparison with previous reported β-diketone Dy(III) analog, the ligand field of 5,6-DTFI is able to induce and enhance the magnetic anisotropy of Dy(III) ion in complex 1.•Moreover, the substituent group in ligand play essential role on regulating the anisotropy barriers.A series of three β-diketone mononuclear lanthanide complexes, namely, Dy(5,6-DTFI)3(H2O)2·H2O2CH2Cl2 (1), Tb(5,6-DTFI)3(H2O)2·H2O2CH2Cl2 (2) and Ho(5,6-DTFI)3(H2O)2·H2O2CH2Cl2 (3) (5,6-DTFI = 5,6-dimethoxy-2-(2,2,2-trifluoroethyl)-1-indone) have been isolated by reactions of 5,6-DTFI and LnCl3·6H2O (Ln = Dy, Tb, Ho). X-ray crystallographic analysis reveals that complexes 1–3 are all eight-coordinated mononuclear structures. Magnetic studies indicate that complex 1 is of single-molecule magnetic behaviors under 0 Oe. Notably, the ligands play essential role on regulating their magnetism. The corresponding structural and magnetic parameters have been discussed in details.A series of three eight-coordinated β-diketone mononuclear lanthanide complexes with LnCl3·6H2O (Ln = Dy, Tb, Ho) exhibit unique anisotropy energy barriers dominated by substituent group in ligand.Download high-res image (63KB)Download full-size image
Co-reporter:Yanping Dong, Pengfei Yan, Xiaoyan Zou, Xu Yao, Guangfeng Hou and Guangming Li
Dalton Transactions 2016 vol. 45(Issue 22) pp:9148-9157
Publication Date(Web):29 Apr 2016
DOI:10.1039/C6DT00442C
A series of four indole-derivative β-diketone mononuclear dysprosium complexes, namely, Dy(EIFD)3(bpy)·CH3CN (1), Dy(EIFD)3(phen)·CH2Cl2 (2), Dy(EIFD)3(dpq)·CH2Cl2 (3), and Dy(EIFD)3(dppz)·2H2O (4) (EIFD = 1-(1-ethyl-1H-indol-3-yl)-4,4,4-trifluorobutane-1,3-dione, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dpq = dipyrazine[2,3-f:2′,3′-h]quinoxaline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine) have been isolated by reactions of EIFD, DyCl3·6H2O and a series of auxiliary ligands. X-ray crystallographic analysis reveals that complexes 1–4 are all eight-coordinated mononuclear structures. Magnetic studies indicate that complexes 1–4 are all single-molecule magnets. Notably, the auxiliary ligands play an essential role in regulating their magnetism. The corresponding structural and magnetic parameters have been discussed in detail.
Co-reporter:Jing-Wen Sun, Peng-Fei Yan, Guang-Hui An, Jing-Quan Sha, Cheng Wang and Guang-Ming Li
Dalton Transactions 2016 vol. 45(Issue 4) pp:1657-1667
Publication Date(Web):08 Dec 2015
DOI:10.1039/C5DT04094A
To investigate the influence of POM species, temperature and counterions on the structures of POM-MOFs containing Cu-tda second building units (SBUs), six new complexes with various dimensionalities, e.g. three dimensional (3D) [Cu(H2tda)(H2O)2]4[SiW12O40]·12H2O (1), two dimensional (2D) [Cu2(H2tda)2(H2O)3]·[Cu(H2tda)(H2O)2]·[PMo12O40]·5H2O (2), H-bond 2D [Cu(H2tda)(H2O)2]3·[PMo12O40]·[Cu(Htda)(H2O)3]·8H2O (3), one dimensional (1D) [Cu2(H2tda)2(H2O)4]2·[Cu2(tda)2(H2O)4]·[HPW12O40]·5H2O (4), 1D [Cu2(H2tda)2(H2O)4][SiW12O40]·(TMA)2·3H2O (5), and zero dimensional (0D) [Cu(H2tda)(H2O)3][SiW12O40]·(TMA)3·H2O (6), were isolated depending on the reaction conditions. It is observed that the POM species, temperature and counterions exhibit an essential effect on the structures, which results in the formation of various dimensional POM-MOF complexes 1–6. In addition, photocatalytic degradation of RhB by complexes 1, 5 and 6 under UV irradiation was also investigated.
Co-reporter:Jing-Wen Sun, Shang-Ju Li, Peng-Fei Yan, Xu Yao and Guang-Ming Li
CrystEngComm 2016 vol. 18(Issue 17) pp:3079-3085
Publication Date(Web):21 Mar 2016
DOI:10.1039/C6CE00182C
Reactions of LnCl3·6H2O (Ln = La, Ce, Pr, Nd, Gd and Lu), L-dibenzoyl tartaric acid (L-DBTA) and triethylamine in a methanol–water solution afford four complexes 1a–4a with 1D ladder chain structures, e.g. {[Ln2(L-DBTA)3(CH3OH)x(H2O)y]·zH2O}n (x = 3 or 4, y = 3 or 4, z = 2 or 5; Ln = La (1a), Ce (2a), Pr (3a) and Nd (4a)) and two complexes 5 and 6 with 1D linear chain structures, e.g. {Et3NH[Ln(L-DBTA)2(CH3OH)2(H2O)2]·2H2O}n (Ln = Gd (5) and Lu (6)). Accidentally, an in situ irreversible SCSC transformation from the kinetically stabilized 1D ladder chain structures of 1a–4a to thermodynamically stabilized 1D linear chain structures of 1–4 was observed, which was seldom reported for lanthanide coordination polymers. The coordination stability around a lanthanide cation was investigated to expatiate on the irreversible SCSC transformation. The solid-state NIR luminescence for complexes 3a, 3, 4a and 4 was also studied.
Co-reporter:Bowen Fei, Pengfei Yan, Tianqi Liu, Fan Yang, Guangming Li
Journal of Luminescence 2016 Volume 177() pp:380-386
Publication Date(Web):September 2016
DOI:10.1016/j.jlumin.2016.04.054
A series of five rigid hexadentate salen-type (H2L) erbium complexes, namely, [Er2L(OAc)4(CH3OH)2]·2CH3OH (1), [Er2L3(CH3OH)]·2CH3OH (2), [Er3L3(OAc)3]·3CH3OH·H2O (3), [Er2L(acac)4]·2CH2Cl2 (4) and [Er2LL′L″(CH3OH)(H2O)2](ClO4)2·CH3OH·H2O (5) (H2L = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine, HL′=2-(2′-hydroxy-3′-methyloxy-phenyl)-benzimidazole and HL″=3-methoxysalicylaldehyde) have been isolated by reactions of H2L with various Er(III) salts. X-ray crystallographic analyses demonstrate that complexes 1, 2, 4 and 5 possess the unique Er2 core with a ratio of H2L/Er=1:2, 3:2, 1:2 and 1:1, respectively. Complex 3 is trinuclear with sandwich-type structure. All complexes 1–5 exhibit near-IR luminescence of Er(III) ions around 1530 nm with lifetime (2.45 μs), which can be rationalized on the basis of the disparate structural effects.
Co-reporter:Wan-Ying Niu, Chang Feng, Nai-ying Fan, Xin-Yu Wang, Peng-Fei Yan, Jing-Wen Sun, Guang-Ming Li
Synthetic Metals 2016 Volume 221() pp:319-325
Publication Date(Web):November 2016
DOI:10.1016/j.synthmet.2016.09.008
•A series of four neodymium coordination polymers have been isolated.•All complexes feature one-dimensional chain structure.•All complexes exhibit characteristic NIR luminescence.A series of four neodymium coordination polymers (CPs), namely, {[Nd2L3(CH3OH)3(H2O)4]}n(1), {[Nd2L3(CH3OH)4(H2O)3]·4CH3OH·H2O}n(2), {[Nd2L3(CH3OH)4(H2O)3]·4CH3OH·H2O}n(3) and [NdL'3(CH3OH)3]n(4) have been isolated by facile reactions of ligands (H2L = L-di-2-thenoyltartaric acid and H2L' = L-di-p-toluoyl-tartaric acid) with NdCl3·6H2O at ambient temperature depending on the reaction conditions. X-ray crystallographic analysis reveals that all complexes 1–4 feature one-dimensional (1D) network structure in which the Nd3+ ions are bridged by carboxylate groups of ligands by five types of coordinated modes. Complexes 1–3 feature one-dimensional (1D) ladder-like chain structure and complex 4 features one-dimensional (1D) linear structure owing tothe ligands coordination modes. NIR luminescence analysis reveal that all complexes 1–4 exhibit three characteristic bands around 890, 1054 and 1326 nm of Nd3+ ion in which complex 3 shows the longest lifetime and highest quantum yield. The energy transfer processes among ligands, the Nd3+ ion and the auxiliary ligand in complexes 1–4 has been investigated.L-di-2-thenoyltartaric acid and L-di-p-toluoyl-tartaric acid lanthanide coordination polymers with one-dimensional chain structures present characteristic near-infrared luminescence of Nd3+ ions.
Co-reporter:Wan-Ying Niu;Jing-Wen Sun; Peng-Fei Yan;Dr. Yu-Xin Li;Dr. Guang-Hui An ; Guang-Ming Li
Chemistry – An Asian Journal 2016 Volume 11( Issue 4) pp:
Publication Date(Web):
DOI:10.1002/asia.201501191
Abstract
A series of five l-di-p-toluoyl-tartaric acid (l-DTTA) lanthanide coordination polymers, namely {[Ln4K4 L6(H2O)x]⋅yH2O}n, [Ln=Dy (1), x=24, y=12; Ln=Ho (2), x=23, y=12; Ln=Er (3), x=24, y=12; Ln=Yb (4), x=24, y=11; Ln=Lu (5), x=24, y=12] have been isolated by simple reactions of H2L (H2L= L-DTTA) with LnCl3⋅6 H2O at ambient temperature. X-ray crystallographic analysis reveals that complexes 1–5 feature two-dimensional (2D) network structures in which the Ln3+ ions are bridged by carboxylate groups of ligands in two unique coordinated modes. Luminescent spectra demonstrate that complex 1 realizes single-component white-light emission, while complexes 2–4 exhibit a characteristic near-infrared (NIR) luminescence in the solid state at room temperature.
Co-reporter:Yanping Dong, Pengfei Yan, Xiaoyan Zou, Tianqi Liu and Guangming Li
Journal of Materials Chemistry A 2015 vol. 3(Issue 17) pp:4407-4415
Publication Date(Web):23 Mar 2015
DOI:10.1039/C5TC00321K
A series of four β-diketone mononuclear dysprosium complexes, namely, Dy(EIFD)3(H2O)·CH2Cl2 (1), Dy(EIFD)3(DMF)·CH2Cl2 (2), Dy(EIFD)3(DMSO) (3), and Dy(EIFD)3(TPPO) (4) (EIFD: 1-(1-ethyl-1H-indol-3-yl)-4,4,4-trifluorobutane-1,3-dione, TPPO: triphenylphosphine oxide), have been isolated by the reactions of a newly designed β-diketone EIFD, DyCl3·6H2O and DMF, DMSO, TPPO, respectively. X-ray crystallographic analysis reveals that complexes 1–4 are isomorphic mononuclear structures in which the Dy(III) ion is rarely seven-coordinated with C3v geometry. Magnetic studies indicate that all complexes 1–4 are single-molecule magnets. The correlations between magnetism and the distortion of the coordination symmetry around the Dy(III) ions have been investigated. Notably, the quantum tunneling of magnetization (QTM), which universally exists in the lanthanide complexes, has been effectively suppressed in this system more related to the less deviation from the ideal C3v symmetry.
Co-reporter:Fang Luan; Tianqi Liu; Pengfei Yan; Xiaoyan Zou; Yuxin Li;Guangming Li
Inorganic Chemistry 2015 Volume 54(Issue 7) pp:3485-3490
Publication Date(Web):March 23, 2015
DOI:10.1021/acs.inorgchem.5b00061
A series of three salen-type lanthanide complexes, e.g., [Dy4(L)2(HL)2Cl2(μ3-OH)2]2Cl2(OH)2·3CH3CH2OH·H2O (1) and [Ln4(L)2(HL)2Cl2(μ3-OH)2]Cl2·5CH3OH·4CH2Cl2 (Ln = TbIII, 2; HoIII, 3) have been isolated by the reactions of H2L (H2L = N,N′-bis(3-methoxysalicylidene)cyclohexane-1,2-diamine) with LnCl3·6H2O. X-ray crystallographic analysis reveals that all complexes 1–3 are isostructural, in which four Ln ions and eight O atoms form the distorted defective dicubane {Dy4O8} cores. Magnetic studies indicate that complex 1 exhibits two slow magnetic relaxation processes with effective energy barrier Ueff = 55.71 K under a zero direct-current field, which is attributed to the two coordination geometries of the DyIII ions with a salen-type ligand and coordination of a chloride counterion. It represents the highest energy barrier among the salen-type tetranuclear lanthanide single-molecule magnets.
Co-reporter:Tian-Qi Liu; Peng-Fei Yan; Fang Luan; Yu-Xin Li; Jing-Wen Sun; Chuan Chen; Fan Yang; Han Chen; Xiao-Yan Zou;Guang-Ming Li
Inorganic Chemistry 2015 Volume 54(Issue 1) pp:221-228
Publication Date(Web):December 11, 2014
DOI:10.1021/ic502194d
A series of rigid hexadentate salen-type (H2L) ytterbium complexes, namely, [Yb2L3(CH3OH)]·3CH3CN (1), [Yb2LL′L″(CH3OH)(H2O)2](ClO4)2·CH3OH·H2O (2), [Yb2L(OAc)4(CH3OH)2]·2CH3OH (3), and {[Yb2L(OAc)4]·3H2O}n (4) (H2L = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine, HL′ = 2-(2′-hydroxy-3′-methyloxy-phenyl)benzimidazole and HL” = 3-methoxysalicylaldehyde) have been synthesized by reactions of H2L with multifarious Yb3+ salts. X-ray crystallographic analyses demonstrate that complex 1 is of a triple-decker sandwich-type Yb2L3 structure with a ratio of H2L/Yb = 3:2, 2 and 3 possess the unique Yb2 core with a ratio of H2L/Yb = 2:2 and 1:2, respectively, 4 exhibits one dimensional coordination polymers in which the polymeric structures are formed by acetate (OAc–) groups. All complexes 1–4 exhibit near-IR luminescence, which can be rationalized on the basis of the disparate structural effects. The magnetic analysis unveils that all complexes 1–4 are of field-induced single-molecule magnet behavior with the energy barriers (Ueff/kB) of 14.5, 2.0, 9.5, and 2.4 K at 3 kOe direct current fields, respectively.
Co-reporter:Fengming Zhang, Xiaoyan Zou, Pengfei Yan, Jingwen Sun, Guangfeng Hou, and Guangming Li
Crystal Growth & Design 2015 Volume 15(Issue 3) pp:1249-1258
Publication Date(Web):January 19, 2015
DOI:10.1021/cg501644z
One Ag+ homometallic complex [Ag4(pzdc)2]·H2O (1), and five Ln–Ag heterometallic complexes, namely, [Gd2Ag6(pzdc)6(H2O)9]·8H2O (2) and [LnAg(pzdc)2(H2O)2]·2H2O [Ln = Tb (3), Dy (4), Ho (5), Er (6)] based on pyrazine-2,3-dicarboxylate (pzdc2–) have been synthesized under room temperature. Complex 1 exhibits 3D metal–organic framework by Ag2 ions connecting 1D square columns consisting of Ag1 ions and pzdc2– ligands, possessing a unique trinodal net with {42·6}{43}{45·64·83·103} topology. Complex 2 displays a 3D heterometal–organic framework with a novel 12-nodal topological net constructed by Gd1 ions linking the adjacent Ag-pzdc2– anion layers. Complexes 3–6 are isostructural 2D Ln–Ag heterometallic coordination frameworks featuring uninodal 4-connected net with {44·62} topology. Magnetic analyses suggest that complexes 4 and 6 exhibit field-dependent slow magnetic relaxation, and complex 6 represents the first slow magnetic relaxation behavior existing in Er3+-based 2D heterometallic coordination framework.
Co-reporter:Fang Luan, Pengfei Yan, Jing Zhu, Tianqi Liu, Xiaoyan Zou and Guangming Li
Dalton Transactions 2015 vol. 44(Issue 9) pp:4046-4053
Publication Date(Web):09 Jan 2015
DOI:10.1039/C4DT02607A
Four isomorphic tetranuclear lanthanide complexes, namely [Ln4(L)2(HL)2(NO3)2(OH)2](NO3)2·4H2O (Ln = Dy (1); Tb (2); Ho (3); Er (4)), constructed using hexadentate salen-type ligand N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine, have been isolated. X-ray crystallographic analysis reveals that all of the complexes 1–4 are of discrete tetranuclear structure with a unique {Ln4O8} core in which four lanthanide ions are coplanar in a rhombic frame. There are two crystallographically unequivalent lanthanide ions, that is the Ln1III ion which is nine-coordinated in a monocapped square-antiprismatic geometry of the C4v point group and the Ln2III ion which is eight-coordinated in a distorted bicapped trigonal-prismatic geometry of the C2v point group. Magnetic analysis reveals that complex 1 exhibits two slow magnetic relaxations with the highest energy barrier among the reported tetranuclear salen-type dysprosium SMMs. This further extends the available SMMs of salen-type lanthanide complexes.
Co-reporter:Guanghui An, Pengfei Yan, Jingwen Sun, Yuxin Li, Xu Yao and Guangming Li
CrystEngComm 2015 vol. 17(Issue 24) pp:4421-4433
Publication Date(Web):21 Apr 2015
DOI:10.1039/C5CE00402K
The racemate-to-homochiral approach is a method to transform or separate a racemic mixture into homochiral compounds. This protocol, if without an external chiral source, is categorized into chiral symmetry breaking. The resolution processes without chiral induction are highly important for the investigation of the origin of homochirality in life, pharmaceutical synthesis, the chemical industry and materials science. Besides the studies on the models and mechanisms used to explain the racemate-to-homochiral approach which may give the probable origin of homochirality in life, recent developments in this field have been plotted towards the separation of enantiomers for the synthesis of pharmaceuticals and chiral chemicals. Direct synthesis of chiral metal–organic framework (MOF) coordination polymers has been achieved as well. In this highlight, we will disclose the comparison of spontaneous resolution and chiral symmetry breaking resolution, and describe the evolution of models and mechanisms for chiral symmetry breaking resolution and its applications in enantiomer resolution and materials science.
Co-reporter:Chang Feng, Jing-Wen Sun, Peng-Fei Yan, Yu-Xin Li, Tian-Qi Liu, Qing-Yan Sun and Guang-Ming Li
Dalton Transactions 2015 vol. 44(Issue 10) pp:4640-4647
Publication Date(Web):19 Jan 2015
DOI:10.1039/C4DT03457K
A series of L-di-2-thenoyltartaric acid lanthanide coordination polymers, namely, {[La2L3(CH3OH)6(H2O)]·CH3OH·H2O}n (1), {[Ln2L3(CH3OH)x(H2O)6−x]·aCH3OH·bH2O}n, [Ln = Eu (2), x = 2, a = 0.5, b = 0.25; Ln = Gd (3), x = 3, a = 1, b = 0; Ln = Tb (4), x = 2, a = 1, b = 0], {[(Eu0.037Tb0.963)2L3(CH3OH)2(H2O)4]·CH3OH·2.75H2O}n (5), {[(Eu0.051Tb0.406La0.543)2L3(CH3OH)2(H2O)4]·0.5CH3OH·2H2O}n (6), and {[(Eu0.068Tb0.363Gd0.569)2L3(CH3OH)3(H2O)3]·CH3OH·H2O}n (7), have been synthesized using facile reactions of H2L (H2L = L-di-2-thenoyltartaric acid) with LnCl3·6H2O under ambient temperature. X-ray crystallographic analysis reveals that complexes 1–4 are isostructural, featuring one-dimensional (1D) ladder-like chain structures, in which the Ln3+ ions are bridged by the carboxylate groups of the ligands. The luminescent spectra in the solid state at room temperature reveal that complexes 2 and 4 exhibit the characteristic red and green luminescence of Eu3+ and Tb3+ ions, respectively, whereas complexes 1 and 3 display the blue emission of the ligand with a broad band centered at 422 nm. Notably, the mixed-lanthanide coordination polymers 5–7 exhibit color-tunable luminescence from yellow and white to blue upon variation of the excitation wavelength. It realizes color-tunable and white-light emission in 1D carboxylic acid mixed-lanthanide coordination polymers.
Co-reporter:Qingyan Sun, Pengfei Yan, Wanying Niu, Wenyi Chu, Xu Yao, Guanghui An and Guangming Li
RSC Advances 2015 vol. 5(Issue 81) pp:65856-65861
Publication Date(Web):27 Jul 2015
DOI:10.1039/C5RA12954K
A series of five β-diketone erbium complexes with various azacyclo-auxiliary ligands, namely, Er(Hbta)3(H2O)2 (1), Er(Hbta)3(bpy) (2), Er(Hbta)3(phen) (3), Er(Hbta)3(dpq) (4) and Er(Hbta)3(dppz) (5) (Hbta = benzoyltrifluoroacetone, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dpq = pyrazino[2,3-f][1,10]phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine) have been isolated and characterized by X-ray crystallographic analysis. Near-infrared luminescence analysis reveals that all complexes 1–5 exhibit strong NIR luminescence of Er(III) ions around 1535 nm with the highest lifetime of 4.532 μs, quantum yield of 3.24 × 10−4 and broadband emission around 1.5 μm for complex 5, in which the azacyclo-auxiliary ligand absorbs and transfers the energy leading to complete quenching of the ligand-associated visible emission. The energy transfer processes among benzoyltrifluoroacetone, the Er(III) ion and the auxiliary ligands in complexes 1–5 have been investigated.
Co-reporter:Xiaoyan Zou, Pengfei Yan, Yanping Dong, Fang Luan and Guangming Li
RSC Advances 2015 vol. 5(Issue 117) pp:96573-96579
Publication Date(Web):03 Nov 2015
DOI:10.1039/C5RA18244A
Two salen type dinuclear dysprosium complexes, namely [Dy(H2L) (NO3)3]2·CH2Cl2·CH3OH·H2O (1) and [Dy(H2L1)2(NO3)3]2·2CH2Cl2·2CH3OH (2) [H2L = N,N′-(1,3-propylene)bis(3-methoxysalicylideneimine) and H2L1 = N,N′-(1,3-propylene)bis(salicylideneimine)], were isolated from the reactions of Dy(NO3)3·6H2O with two different but similar salen type ligands (H2L and H2L1), respectively. X-ray crystallographic analyses revealed that two crystallographically equivalent Dy(III) ions for 1 and two crystallographically non-equivalent Dy(III) ions for 2 were both bridged by two ligands displaying broken hula hoop-like and hula hoop-like coordination geometries for complexes 1 and 2, respectively, which resulted in the distinct magnetic properties that complex 2 exhibited with relatively higher energy barriers under a 2 kOe dc field.
Co-reporter:Wenyi Chu, Qingyan Sun, Xu Yao, Pengfei Yan, Guanghui An and Guangming Li
RSC Advances 2015 vol. 5(Issue 115) pp:94802-94808
Publication Date(Web):30 Oct 2015
DOI:10.1039/C5RA17358B
A series of three luminescent single molecule magnets of β-diketone mononuclear dysprosium complexes, namely, Dy(tfa)3(H2O)2·Me2CO (1), Dy(tfa)3(bpy) (2) and Dy(tfa)3(phen) (3) (tfa = trifluoroacetylacetonate, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, C3H6O = Me2CO) have been isolated. Single-crystal X-ray analysis shows all the central Dy(III) ions are eight-coordinated adopting the coordination geometries of the distorted dodecahedron, bicapped trigonal prism and square antiprism for complexes 1–3, respectively. Magnetic analyses exhibit slow magnetic relaxation with the barrier heights (Ueff/kB) of 41 K, 33 K and 55 K for complexes 1–3, respectively. Photo-luminescent analysis reveal that complexes 1–3 exhibit the typical yellow luminescence of Dy(III) ions. The correlation between the structure and physical properties has been investigated.
Co-reporter:Yumei Yue, Pengfei Yan, Jingwen Sun, Guangming Li
Inorganic Chemistry Communications 2015 Volume 54() pp:5-8
Publication Date(Web):April 2015
DOI:10.1016/j.inoche.2015.01.031
•Variable-temperature dc magnetic susceptibility shows antiferromagnetic interactions between Dy(III) centers.•The dynamic susceptibility exhibits a typical of SMM behavior.•The complex has dinuclear units with a rare μ2-(OCH3)2 bridge.•We report a Salen-type dysprosium complex representing pure 4f SMMs with a flexible 2D polymeric coordination network.A new flexible Salen-type dysprosium coordination polymer, [Dy2(H2L)2(NO3)4(CH3O)2]n (1) (H2L = N,N′-bis(salicylidene)-1,4-butane-diamine), has been synthesized by a solvothermal method. The single-crystal X-ray diffraction studies reveal that complex 1 features a two dimension (2D) network structure with rare dinuclear units. Each Dy(III) ion is eight-coordinated where the μ2-(OCH3)2 bridged Dy2O2 cores are linked by four Salen-type ligands in bidentate fashion. Magnetic studies reveal that complex 1 presents antiferromagnetic interactions between Dy(III) centers and exhibits the frequency dependent peaks, a behavior characteristic of a single-molecule magnet.The flexible Salen-type dysprosium complex represents 4f SMMs with the 2D coordination networks from rare methoxy-O bridged dinuclear units.
Co-reporter:Yumei Yue, Jingwen Sun, Pengfei Yan, Guangming Li
Inorganic Chemistry Communications 2015 Volume 51() pp:42-45
Publication Date(Web):January 2015
DOI:10.1016/j.inoche.2014.11.007
•Variable-temperature dc magnetic susceptibility shows weak long-range order of chain of magnetization.•The dynamic susceptibility exhibits a typical of SMM behavior.•The Cole–Cole curves show the presence of at least two relaxation processes at a low temperature.•We report a Salen-type dysprosium complex that represents pure 4f SIMs with 1D ionic coordination network.A new flexible Salen-type dysprosium coordination polymer, e.g. {[Dy2(H2L)4Cl4(CH3OH)2]Cl2·CH3OH}n (1) (H2L = N,N′-bis(salicylidene)-1,4-butane-diamine), is afforded by the reaction of H2L with DyCl3·6H2O. X-ray crystallography analysis reveals that complex 1 features one-dimensional (1D) ionic double-chain structure. Magnetic studies suggest that the coordination polymer exhibits a typical SMM behavior under an external magnetic field.The flexible Salen-type dysprosium complex with 1D ionic coordination network represents the 4f SIMs.
Co-reporter:Dan-Dan Ding, Ting Gao, Ou Sun, Guang-Ming Li, Yu-Hong Wu, Miao-Miao Xu, Xiao-Yan Zou, Peng-Fei Yan
Inorganic Chemistry Communications 2015 Volume 51() pp:21-25
Publication Date(Web):January 2015
DOI:10.1016/j.inoche.2014.11.001
•Two heteropolynuclear Schiff-base complexes were synthesized.•Both complexes form similar 1D ladder-like structure.•Magnetic properties of obtained complexes were determined.Two new complexes [{CuL}Sm(H2O)3{Fe(CN)6}]2·6H2O (1) [{CuL}2Pr(H2O){Fe(CN)6}]2·4H2O (2) (H2L = N,N′-ethylenebis(3-methoxysalicylideneimine)) have been prepared by reactions of acyclic compartmental Schiff-base heterodinuclear 3d–4f compound [{CuL}Ln(NO3)3] (Ln = Sm & Pr) with K3[Fe(CN)6]. Crystal structures of both 1 and 2 reveal unique topology structures. 1 shows a dimeric heterotrinuclear [{CuL}Sm(H2O)3{Fe(CN)6}]2 while 2 displays a dimeric heterotetranuclear [{CuL}2Pr(H2O){Fe(CN)6}] with distorted sandwich moieties [{CuL}2Pr]. Both 1 and 2 form similar 1D ladder-like structure through the intermolecular double bridges of Cu–N bonds. The measurement of variable-temperature magnetic susceptibility reveals that both complexes 1 and 2 exhibit antiferromagnetic interaction between spin carriers.Two heteropolynuclear Schiff-base complexes have been prepared by reactions of acyclic compartmental Schiff-base heterodinuclear 3d-4f compound [{CuL}Ln(NO3)3] with K3[Fe(CN)6]. Both complexes exhibit antiferromagnetic interaction between spin carriers.
Co-reporter:Tian-Qi Liu, Peng-Fei Yan, Fang Luan, Jing-Wen Sun, Guang-Ming Li
Synthetic Metals 2015 Volume 209() pp:377-382
Publication Date(Web):November 2015
DOI:10.1016/j.synthmet.2015.08.007
•Two hetero-metallic complexes supported by salen-type and β-diketonate ligands.•The Ln3+ ion is of a typical double-decker sandwich structure.•Both of complexes 1 and 2 exhibit single molecule magnet behaviour.•The energy barrier of complex 1 is 40.1 K under an optimal external field.Two new hetero-metallic complexes [LnNa2(L)2(bta)(CH3OH)]∙nH2O∙mCH3OH (Ln = Dy (1), n = 1, m = 0; Er (2), n = 0, m = 1) supported by rigid hexadentate salen-type (H2L = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine) and β-diketonate (bta = benzoyltrifluoroacetone) ligands have been designed and synthesized. Structural analysis reveals that the Ln3+ ion has a typical double-decker sandwich structure with a distorted bicapped triangular prism. The magnetic analysis unveils that both complexes 1 and 2 are of single molecule magnet behavior, and both of them can be regarded as rare SMMs based on the salen-type ligand with a double-decker structure.
Co-reporter:Jing Zhu, Changzheng Wang, Fang Luan, Tianqi Liu, Pengfei Yan, and Guangming Li
Inorganic Chemistry 2014 Volume 53(Issue 17) pp:8895-8901
Publication Date(Web):August 19, 2014
DOI:10.1021/ic500501r
A series of three β-diketone mononuclear dysprosium complexes, namely, Dy(TFI)3(H2O)2 (1), Dy(TFI)3(bpy) (2), and [Dy(TFI)3(Phen)]·0.02CHCl3 (3) (TFI = 2-(2,2,2-trifluoroethyl)-1-indone, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been designed and synthesized. Crystal structure analysis reveals that complexes 1–3 have haveisomorphic structures in which the central Dy(III) ion is eight-coordinated by six oxygen atoms from three TFI ligands and two O/N atoms from auxiliary ligands, forming a distorted bicapped trigonal prismatic geometry for 1, a distorted dodecahedral geometry for 2, and a distorted square antiprismatic geometry for 3, respectively. Magnetic studies indicate that complex 2 with D2d symmetry and 3 with D4d symmetry exhibit slow magnetic relaxation with barrier heights (Ueff/kB) of 48.8 K for 2 and 57.9 K for 3. Strikingly, the relaxation time (τ) of 0.0258 s for 3 is about 20 times that for 2, which is presumably associated with larger rotation of the SAP surroundings for 3. Further, complexes 2 and 3 exhibit essential magnetic hysteresis loops at 1.8 K. These extend the recent reports of the single-ion magnets (SIMs) of β-diketone mononuclear dysprosium complexes.
Co-reporter:Jing-Wen Sun, Jing Zhu, Hui-Feng Song, Guang-Ming Li, Xu Yao, and Peng-Fei Yan
Crystal Growth & Design 2014 Volume 14(Issue 11) pp:5356-5360
Publication Date(Web):October 23, 2014
DOI:10.1021/cg501211f
A series of three 3D homochiral lanthanide–organic frameworks {[Ln(H2LSS)(NO3)2Cl]·2CH2Cl2}n [Ln = La (1), Ce (2), and Nd (3)] with the unique diamond (dia) topology have been obtained by utilizing racemic salen-type ligand and mixed lanthanide salts. Complexes 1–3 are isostructural, crystallizing in the chiral tetragonal space group P43212 and adopting an individual dia network formed by lanthanide ions and bridging ligand trans-N,N′-bis(salicylidene)-(1S,2S)-cyclohexanediamine (H2LSS). This “from racemate to homochiral” approach may point to a new avenue for the preparation of homochiral materials.
Co-reporter:Fengming Zhang, Pengfei Yan, Xiaoyan Zou, Juwen Zhang, Guangfeng Hou, and Guangming Li
Crystal Growth & Design 2014 Volume 14(Issue 4) pp:2014-2021
Publication Date(Web):March 3, 2014
DOI:10.1021/cg5001254
Three novel alkali–lanthanide heterometal–organic frameworks, namely, [K5Ln5(pztc)5(H2O)19]·7H2O [Ln = Dy (1), Ho (2), and Yb (3); H4pztc = pyrazine-2,3,5,6-tetracarboxylic acid], have been facilely synthesized. X-ray crystallographic analysis reveals that complexes 1–3 are isostructural, featuring unique 3D open frameworks, which possess a rare (4,8)-connected net with the Schläfli symbol of (415·612·8)(45·6)2. The 3D coordination framework involves a ladder-like square column structure by pztc4– ligands bridging metal ions, exhibiting 1D channels along the b axis. The magnetic analysis suggests that complexes 1 and 3 exhibit frequency-dependent out-of-phase signals in alternating current magnetic susceptibility measurements, indicating their slow magnetic relaxation characteristics. It is the first report of slow magnetic relaxation behavior existing in Yb3+-based HMOFs.
Co-reporter:Fengming Zhang, Pengfei Yan, Hongfeng Li, Xiaoyan Zou, Guangfeng Hou and Guangming Li
Dalton Transactions 2014 vol. 43(Issue 33) pp:12574-12581
Publication Date(Web):22 May 2014
DOI:10.1039/C4DT00837E
A series of pyrazine-2,3,5,6-tetracarboxylate alkali–lanthanide coordination frameworks, namely [NaLn(pztc)(H2O)3]·H2O [Ln = Ce (1), Sm (2), Eu (3), Gd (4) and Tb (5); H4pztc = pyrazine-2,3,5,6-tetracarboxylic acid], have been synthesized by reacting Ln(NO3)3·6H2O with H4pztc in the presence of NaOH at room temperature. X-ray crystallographic analysis reveals that complexes 1–5 are isostructural, featuring three-dimensional (3D) networks with a unique (411·68·82)(43·62·8)(43) topology in which the ligand displays a novel μ7-coordination mode. The photoluminescence (PL) spectra in the solid state reveal that complexes 2, 3 and 5 exhibit the characteristic luminescence of Sm(III), Eu(III) and Tb(III) ions, respectively, while complex 4 displays a broad band in the range of 400–650 nm (λmax = 505 nm) which exhibits about 103 nm red-shift and enhancement compared to the band of the free ligand. Further, the isostructural two-component Eu(III)-doped Gd(III) complexes realize color-tunable luminescence from red to yellow, white, green and blue by the variation of excitation wavelengths. They represent the first example of full-color-tunable emission in lanthanide coordination frameworks by the variation of excitation light.
Co-reporter:Daniel M. Pajerowski, Quan Li, Jason Hyun, Cindi L. Dennis, Daniel Phelan, Pengfei Yan, Peng Chen and Guangming Li
Dalton Transactions 2014 vol. 43(Issue 31) pp:11973-11980
Publication Date(Web):27 Jun 2014
DOI:10.1039/C4DT01329H
Three chloride-bridged lanthanide compounds, [Ln4Cl6(CH3OH)12(OH)2]·4Cl·2CH3OH [Ln = Gd (1), Dy (2) and Er (3)], have been unexpectedly isolated by the reactions of LnCl3·6H2O and N,N′-bis(salicylidene)-1,2-(phenylene-diamine) (H2L). X-ray crystallographic analysis reveals a triclinic cell with a unique defect-dicubane {Ln4} core and the structure across this series is nominally isomorphic. Measurements of direct current magnetic susceptibility and isothermal magnetization give insight into the relevant cluster Hamiltonians for 1, 2, and 3, and alternating current susceptibility shows slow relaxation in 2, but not in 1 or 3 down to 2 K and up to 1 kHz.
Co-reporter:Weizuo Li, Jingya Li, Hongfeng Li, Pengfei Yan, Guangfeng Hou, Guangming Li
Journal of Luminescence 2014 Volume 146() pp:205-210
Publication Date(Web):February 2014
DOI:10.1016/j.jlumin.2013.09.009
•Two series of six β-diketone (TFI) lanthanide complexes have been isolated.•NIR luminescence of the six lanthanide complexes has been investigated.•Intramolecular energy transfer between ligands and Ln3+ (Ln=Nd, Yb) ions are studied.Two series of six β-diketone, 2-(2,2,2-trifluoroethyl)-1-indone (TFI) containing a trifluorinated alkyl group and a rigid indone group, neodymium and ytterbium complexes, namely, [Ln(TFI)3L] [Ln=Nd; L=(H2O)2 (1), bpy (2) and phen (3); Ln=Yb; L=(H2O)2 (4), bpy (5) and phen (6); bpy=2,2-bipyridine, phen=1,10-phenanthroline], have been synthesized and isolated. X-ray crystallographic analysis reveals that complex 2 is mononuclear structure in which the central Nd3+ ion is eight-coordinated by six oxygen atoms furnished by three TFI ligands and two nitrogen atoms from ancillary ligand. PXRD analysis suggests that all complexes 1 and 4, 2 and 5, 3 and 6 are isomorphic, respectively The room-temperature PL spectra of complexes 1–6 show strong characteristic NIR luminescence of the corresponding Nd3+ and Yb3+ ions and the substitution of the solvent molecules by bidentate nitrogen ligands essentially enhance the NIR luminescence quantum yields and lifetimes of the complexes.
Co-reporter:Qiang Li, Yan Wang, Pengfei Yan, Guangfeng Hou, Guangming Li
Inorganica Chimica Acta 2014 Volume 413() pp:32-37
Publication Date(Web):24 March 2014
DOI:10.1016/j.ica.2013.12.032
•Two 7,7,8,8-tetracyanoquinodimethane (TCNQ) Pb2+ and Zn2+ complexes have been isolated.•Complex 1 features a novel 3D structure and complex 2 features a 0D ionic structure.•Their electrochemistry has been investigated and discussed.Two 7,7,8,8-tetracyanoquinodimethane (TCNQ) Pb2+ and Zn2+ complexes, namely, {[Pb2(TCNQ)3(H2O)6](TCNQ)}n (1) and Li[Zn2(TCNQ)5(H2O)6]·[Zn(TCNQ)2(H2O)4]·6H2O (2) have been synthesized by the reactions of Li(TCNQ) with PbCl2 and Zn(TPP)2Cl2 (TPP = Triphenylphosphine), respectively. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 3D network structure and complex 2 features a 0D structure in which a neutral molecule of [Zn(TCNQ)2(H2O)4] crystallizes in the crystal. The flexible coordination modes of TCNQ and the metal ions play essential roles on the formation of the novel 3D structures and the unique 0D ionic structure as well as the TCNQ molecules adapt in one-dimensional column of TCNQ through π–π stacking interactions among the TCNQ metal complexes. Cyclic and differential pulse voltammograms for complexes 1 and 2 show the reversible one-electron oxidation and one-electron reduction within the electrochemical window of CH3CN. Their electrochemical HOMO–LUMO gap and reversibility are examined.Graphical abstractTwo 7,7,8,8-tetracyanoquinodimethane (TCNQ) Pb2+ and Zn2+ complexes featuring unique 3D and 0D structure have been isolated and structurally determined.
Co-reporter:Ju-Wen Zhang, Yan Wang, Peng-Fei Yan, Guang-Feng Hou, Guang-Ming Li
Inorganica Chimica Acta 2014 Volume 416() pp:22-27
Publication Date(Web):24 May 2014
DOI:10.1016/j.ica.2014.03.012
•Seven lanthanide TCNQ complexes were obtained.•The reaction solvent has an important effect on the structures of complexes.•The magnetic and electrochemical properties of complexes were investigated.Reactions between trivalent lanthanide ions and the radical anion of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) produce four mononuclear complexes [Ln(TCNQ)2(H2O)7](TCNQ)·5H2O·EtOH [Ln = Nd (1), Sm (2), Eu (3) and Gd (4)] and three dinuclear complexes [Ln2(TCNQ)2(H2O)15](TCNQ)4·x(p-dioxane)·7H2O [Ln = Ce (5, x = 2.5), Pr (6, x = 2.5) and Nd (7, x = 2)]. One of the coordinated TCNQ− radical anions is involved in π–π stacking interactions with the uncoordinated TCNQ− radical anions, and the other coordinated TCNQ− radical anion is not involved in such π–π interactions in 1–4. All the TCNQ− radical anions are involved in π–π interactions in 5–7. The effect of reaction solvent on the structures of 1–7 was revealed. The magnetic properties of 4 and the electrochemical properties of 1–7 were investigated.Seven lanthanide TCNQ complexes were synthesized. Reaction solvent plays an important role in tuning structures of these seven complexes. Magnetic and electrochemical properties of these seven complexes were investigated.
Co-reporter:Jing Zhu, Huifeng Song, Jingwen Sun, Pengfei Yan, Guangfeng Hou, Guangming Li
Synthetic Metals 2014 Volume 192() pp:29-36
Publication Date(Web):June 2014
DOI:10.1016/j.synthmet.2014.03.011
•Five new salen type lanthanide coordination polymers have been isolated.•Complexes 1 and 5 feature a 1D chain structure and 2–4 feature a 1D ionic spiral chain structure.•Their UV–visible, NIR luminescence, and SHG properties have been studied.A series of five new N,N′-bis(salicylidene)-1,2-cyclohexanediamine (H2L) lanthanide coordination polymers, namely, [Nd(H2L)(NO3)3MeOH]n (1), {[Sm(H2L)Cl2(MeOH)3]Cl·3MeOH}n (2), {[Ln(H2L)Cl2(MeOH)3]Cl·2MeOH}n [Ln = Gd (3) and Er (4)] and {[Lu(H2L)Cl3(MeOH)]·H2O}n (5) have been isolated by reactions of H2L with LnCl3·6H2O and Ln(NO3)3·6H2O, respectively. X-ray crystallographical analysis revealed that H2L effectively functions as a bridging ligand forming a series of 1D linear polymers 1 and 5 as well as 1D spiral polymers 2–4. The luminescence of complexes 1 and 2 has been investigated. Complex 1 exhibits the NIR luminescence of Nd(III) ion and complex 2 exhibits co-luminescence of the ligand and the Sm(III) ions. The lowest triplet level of ligand H2L was calculated on the basis of the phosphorescence spectrum of complex 3. The energy transfer mechanism in the 2 were described and discussed. Strikingly, coordination polymer 5 is SHG active, and the SHG efficiency is 0.4 times as much as that of urea.Five N,N′-bis(salicylidene)-1,2-cyclohexanediamine (H2L) lanthanide coordination polymers featuring unique 1D liner and 1D spiral chain structures exhibit SHG active, NIR luminescence and red emission.
Co-reporter:Qiang Li, Pengfei Yan, Guangfeng Hou, Yan Wang and Guangming Li
Dalton Transactions 2013 vol. 42(Issue 21) pp:7810-7815
Publication Date(Web):18 Mar 2013
DOI:10.1039/C3DT50261A
Three new 7,7,8,8-tetracyanoquinodimethane (TCNQ) alkaline-earth metal complexes, namely {[M2(TCNQ)3(H2O)6]·TCNQ}n (M = Ca (1), Sr (2) and Ba (3)) have been synthesized by salt elimination reactions. X-ray crystallographic analysis reveals that complexes 1, 2 and 3 are isomorphic featuring a unique 3D structure. Cyclic and differential pulse voltammograms for complexes 1–3 show a reversible one-electron oxidation and a reversible one-electron reduction within the electrochemical window of CH3CN. Their electrochemical HOMO–LUMO gap and reversibility are examined.
Co-reporter:Xiaoyan Zou, Mingjie Li, Pengfei Yan, Juwen Zhang, Guangfeng Hou and Guangming Li
Dalton Transactions 2013 vol. 42(Issue 26) pp:9482-9489
Publication Date(Web):04 Apr 2013
DOI:10.1039/C3DT50534K
Two types of N,N′-bis(salicylidene)-1,3-propanediamine (H2L) lanthanide complexes, viz. [Ln(NO3)3(H2L)2]·0.2CH3OH [Ln = La (1), Ce (2) and Pr (3)] and [Ln(NO3)3(H2L)2]2·CH2Cl2·CH3OH [Ln = Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Yb (9)], have been isolated by reactions of H2L with Ln(NO3)3·6H2O. X-ray crystallographic and PXRD analysis reveal that 1–3 are isomorphic possessing a novel one-dimensional (1D) ladder-like double-chain structure. Complexes 4–9 are isostructural exhibiting a discrete dinuclear structure. Luminescent analysis reveals the lanthanide ion and ligand-centered co-luminescence for 5, 6 and 8, which are attributed to the incomplete energy transfer from the triplet state of H2L to the resonance energy level of the corresponding Ln(III) ion. Further, the characteristic near infrared (NIR) luminescence of Nd(III) and Yb(III) ions for complexes 4 and 9 have been revealed.
Co-reporter:Weizuo Li, Pengfei Yan, Guangfeng Hou, Hongfeng Li and Guangming Li
Dalton Transactions 2013 vol. 42(Issue 32) pp:11537-11547
Publication Date(Web):30 May 2013
DOI:10.1039/C3DT50580D
A new β-diketone, 5,6-dimethoxy-2(2,2,2-trifluoroethyl)-1-indone (5,6-DTFI), has been designed and synthesized. Two series of four 5,6-DTFI Sm3+ and Eu3+ complexes, namely, Eu(5,6-DTFI)3(H2O)2 (1), Eu(5,6-DTFI)3(Phen) (2), Sm(5,6-DTFI)3(H2O)2 (3) and Sm(5,6-DTFI)3(Phen) (4) (Phen = 1,10-phenanthroline), have been isolated. X-ray diffraction analysis reveals that all complexes 1–4 are of mononuclear structures. Luminescent and phosphorescent spectra of complexes 1–4 show strong characteristic emissions of the corresponding Eu3+ and Sm3+ ions. Upon complexes 1 and 2 were doped into the poly(methylmethacrylate) (PMMA) forming the films, the PMMA polymer matrix acting as a co-sensitizer for Eu3+ ion enhances the luminescent lifetimes, overall quantum yields and the thermal stability in comparison with the precursor complexes.
Co-reporter:Xiaoyan Zou, Pengfei Yan, Juwen Zhang, Fengming Zhang, Guangfeng Hou and Guangming Li
Dalton Transactions 2013 vol. 42(Issue 36) pp:13190-13199
Publication Date(Web):21 Jun 2013
DOI:10.1039/C3DT51556G
A series of five N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-propanediamine (H2L) ytterbium complexes, namely, [Yb(H2L)2(CH3OH)](ClO4)3 (1), [Yb(H2L)(NO3)3]2·CH2Cl2 (2), [Yb(H2L)2(NO3)]2(PF6)4·4H2O·2CH2Cl2 (3), [Yb(H2L)(OAc)2]2(PF6)2·4CH2Cl2 (4) and [Yb3L′3(OH)2Cl(H2O)5]Cl3·4H2O (5) (HL′ = 2-hydroxy-3-methoxybenzaldehyde), have been synthesized by reactions of H2L with multifarious Yb(III) salts. X-ray diffraction analysis reveals that complex 1 shows a unique mononuclear structure constructed from two chelating H2L ligands in crossover mode. Complex 2 exhibits a dinuclear structure bridged by two H2L ligands. Complexes 3 and 4 possess two novel dinuclear structures linked by NO3− and OAc− anions, respectively. Complex 5 displays a trinuclear structure supported by three L′ and two OH− anions. Noticeable, complex 3 can be transformed from 2 by introducing (NH4)(PF6). The PF6− counterion plays an essential role in steering the structural transformation. The anions dominate the final structures of 1–5. All complexes 1–5 exhibit NIR luminescence, which can be rationalized on the basis of different structural effects. Preliminary catalytic studies reveal that all complexes 1–5 are able to catalyze effectively a typical Henry reaction with good yields.
Co-reporter:Bo Gao, Qian Zhang, Pengfei Yan, Guangfeng Hou and Guangming Li
CrystEngComm 2013 vol. 15(Issue 20) pp:4167-4175
Publication Date(Web):21 Mar 2013
DOI:10.1039/C3CE40207J
A series of five new salen type cerium complexes, namely [Ce(H2L)2CH3OH](PF6)3·2H2O·CH2Cl2 (1), [Ce(IV)L2] (2), [Ce(H2L)(NO3)3CH3OH] (3), [Ce2(H2L)3(NO3)6]·4H2O (4) and {[Ce(H2L)2(NO3)2](PF6)·2CH3CN}n (5) (H2L = N,N′-bis(3-methoxysalicylidene)cyclohexane-1,2-diamine), have been isolated by reactions of H2L with various cerium salts and/or NH4PF6. All complexes 1–5 have been fully characterized by elemental analysis, FT-IR spectroscopy, UV spectroscopy, powder X-ray diffraction, TG–DSC analysis, and single-crystal X-ray diffraction. X-ray crystallographical analysis reveals that complexes 1–3 are of discrete mononuclear structures, 4 is of a discrete binuclear structure, and complex 5 is of a unique quartz 3D topological structure. The electrochemical behavior of this series of salen type cerium complexes has been examined by cyclic voltammetry in acetonitrile. Cyclic voltammograms of complexes 1 and 3–5 show two quasi-reversible redox processes within the electrochemical window of acetonitrile.
Co-reporter:Jing Zhu, Hui-Feng Song, Peng-Fei Yan, Guang-Feng Hou and Guang-Ming Li
CrystEngComm 2013 vol. 15(Issue 9) pp:1747-1752
Publication Date(Web):11 Dec 2012
DOI:10.1039/C2CE26680F
Two salen-type Dy complexes, namely [Dy2L3(CH3OH)] (1) and {[Dy(H2L)Cl2(MeOH)3]Cl·3MeOH}n (2) (H2L = N,N′-bis(salicylidene)-1,2-cyclohexanediamine), have been isolated by the reactions of H2L with Dy(OAc)3·6H2O and DyCl3·6H2O, respectively. X-ray crystallographic analysis reveals that 1 is a dinuclear structure and 2 is a 1D ionic spiral chain structure. Magnetic studies indicate that both complexes 1 and 2 exhibit slow magnetic relaxation, extending the recent reports on pure 4f-type single molecule magnets (SMMs) and single ion magnets (SIMs).
Co-reporter:Ting Gao, Yu Yang, Wen-Bin Sun, Guang-Ming Li, Guang-Feng Hou, Peng-Fei Yan, Ji-Tong Li and Dan-Dan Ding
CrystEngComm 2013 vol. 15(Issue 31) pp:6213-6220
Publication Date(Web):31 May 2013
DOI:10.1039/C3CE40714D
Three dinuclear lanthanide complexes are achieved by using H2salen or H2salen/acac ligands (H2salen = N,N′-ethylenebis(salicylideneimine), acac = acetylacetonate). They are homodinuclear [Er2(salen)3] (1), [Yb2(salen)2(acac)2] (2), and heterodinuclear geometrical [ErYb(salen)2(acac)2] (3). The structures of complexes were determined by single crystal X-ray crystallographic studies and their photophysical properties were investigated. The homonuclear Yb2 complex exhibits characteristic metal-centered NIR emission. The geometric ErYb isomer exhibits ‘dual emissions’ from both erbium(III) and ytterbium(III) ions. There was no detectable photoluminescence in the Er2 complex, not only in solid state but also in solvent.
Co-reporter:Guang-Feng Hou, Hong-Xing Li, Wei-Zuo Li, Peng-Fei Yan, Xiao-Hong Su, and Guang-Ming Li
Crystal Growth & Design 2013 Volume 13(Issue 8) pp:3374-3380
Publication Date(Web):July 8, 2013
DOI:10.1021/cg400174r
Two series of eight polycarboxylate lanthanide coordination complexes, namely, [Ln(cpia)(H2O)2]·4H2O {Ln = Ce (1), Nd (2), and Sm (3)} and [Ln(cpia)(H2O)n]2·2H2O {Ln = Eu (4), Gd (5), Tb (6), Er (7), and Lu (8), n = 5 in 4–7; n = 4 in 8} {H3cpia = N-[4-(carboxymethoxy)phenyl]iminodiacetic acid}, have been synthesized by self-assembly and characterized by IR, thermogravimetric analysis, and X-ray crystallography. Complexes 1–3 are isomorphic featuring two-dimensional double layer structures, while the isomorphic complexes 4–8 exhibit [2 + 2] rectangle metallomacrocycle structures. Further, photoluminescence (PL) spectra of complexes 2, 4, and 6 show the strong characteristic luminescence of Eu(III), Tb(III), and Nd(III) ions, respectively, suggesting that cpia3– is able to efficiently sensitize the luminescence of lanthanide ions.
Co-reporter:Weizuo Li, Pengfei Yan, Guangfeng Hou, Hongfeng Li and Guangming Li
RSC Advances 2013 vol. 3(Issue 39) pp:18173-18180
Publication Date(Web):24 Jul 2013
DOI:10.1039/C3RA41594E
A new β-diketone, 5,6-dimethoxy-2-(2,2,2-trifluoroethyl)-1-indone (5,6-DTFI) and two series of 5,6-DTFI lanthanide complexes, namely, Nd(5,6-DTFI)3(H2O)(CH3OH) (1), Nd(5,6-DTFI)3(phen) (2), Yb(5,6-DTFI)3(H2O)2 (3) and Yb(5,6-DTFI)3(phen) (4) (phen = 1,10-phenanthroline), have been isolated. X-ray diffraction analysis reveals that all complexes 1–3 have mononuclear structures. NIR luminescent spectra of complexes 1–4 show strong characteristic emissions of the corresponding Nd3+ and Yb3+ ions. Upon doping poly(methylmethacrylate) (PMMA) with complex 1 to form a film, the PMMA polymer matrix acts as a co-sensitizer for Nd3+ ion and increases the NIR luminescent lifetimes, overall quantum yields and the thermal stability in comparison with the precursor complex 1.
Co-reporter:Chuan Chen, Han Chen, Pengfei Yan, Guangfeng Hou, Guangming Li
Inorganica Chimica Acta 2013 Volume 405() pp:182-187
Publication Date(Web):24 August 2013
DOI:10.1016/j.ica.2013.05.014
Highlights•Three salen type Ce(IV) complexes have been isolated.•Mononuclear salen type Ce(IV) complexes with sandwich and crossover structures are revealed.•Their electrochemistry has been investigated and discussed.Reactions of N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine (H2L) with different cerium salts, e.g. Ce(OAc)3·5H2O, Ce(NO3)3·6H2O and CeCl3·6H2O, afford three salen type mononuclear Ce(IV) complexes, namely, [Ce(IV)(L)2]·2CH2Cl2 (1), [Ce(IV)(L)2] (2) and (NH4)2[Ce(IV)(L)2](PF6)2 (3). X-ray crystallographic analysis reveals that complexes 1 and 3 are of distorted sandwich mononuclear structures, while complex 2 is of a crossover mononuclear structure. All Ce(IV) ions are eight-coordinated to four imines nitrogen atoms and four oxygen atoms of phenolic hydroxyl groups from two ligands. Complexes 1–3 represent few known salen type cerium complexes with Ce(IV) ions. Cyclic voltammograms and differential pulse voltammograms of complexes 1–3 show a reversible one-electron oxidation and a reversible one-electron reduction within the electrochemical window of CH3CN.Graphical abstractThree new salen type Ce(IV) complexes, have been synthesized and structurally determined. Their electrochemical properties are investigated and discussed.
Co-reporter:Guangfeng Hou, Ruiqiang Ding, Pengfei Yan, Hongfeng Li, Peng Chen, Guangming Li
Synthetic Metals 2013 Volume 164() pp:32-37
Publication Date(Web):15 January 2013
DOI:10.1016/j.synthmet.2012.12.029
Reactions of 3-pyridin-3-yl-benzoic acid (HL1) and 3-pyridin-4-yl-benzoic acid (HL2) with lanthanide nitrate hexahydrate under hydrothermal conditions yield four new coordination polymers, namely [Sm2(L1)6(H2O)4]n (1) and [Ln(L2)3(H2O)2·H2O]n (Ln = Nd (2), Gd (3) and Er (4)). X-ray diffraction analysis reveals that 1 is of one-dimensional (1D) zigzag chain arrays featuring two different lanthanide ion centers. In contrast, complexes 2–4 exhibit 1D linear chain arrays exhibiting only one crystallographically distinct lanthanide ion. In addition, two known complexes [Ln(L2)3(H2O)2·H2O]n (Ln = Eu (5), Tb (6)), are also synthesized as well as their triplet energy-levels are investigated, the results reveal that both complexes 5 and 6 are able to emit intensively characteristic red and green luminescence of the Eu3+ and Tb3+ ions with luminescence lifetime of 386.3 μs and 715.8 μs, respectively. Further, magnetic analysis suggests that complex 3 is of an antiferromagnetic character.Graphical abstractTwo types of four pyridin-yl-benzoic lanthanide coordination complexes featuring 1D chain structure which further packing to 3D network structure by different π–π interactions between different pyridyl and/or phenyl groups.Highlights► A series of lanthanide complexes have been synthesized under hydrothermal conditions. ► Their luminescence are systematically studied. ► Magnetism of complex 3 is investigated.
Co-reporter:Yu Yang;Peng-Fei Yan;Po Gao;Ting Gao
Journal of Inorganic and Organometallic Polymers and Materials 2013 Volume 23( Issue 6) pp:1211-1218
Publication Date(Web):2013 November
DOI:10.1007/s10904-013-9872-3
Two type lanthanide complexes obtained by salen-type ligand N,N’-ethylenebis(salicylideneimine) (H2La) and N,N’-ethylene-bis(3-methoxysalicylideneimine) (H2Lb) have been isolated. They are 2D coordination polymer [Yb(H2La)1.5(NO3)3]n (1), mononuclear Ln(H2Lb)(NO3)3 [Ln = Sm (2), Ho (3)]. The structures of 1–3 were determined by single crystal X-ray crystallographic studies and their photophysical properties were investigated.
Co-reporter:Lili Xu, Qian Zhang, Guangfeng Hou, Peng Chen, Guangming Li, Daniel M. Pajerowski, Cindi L. Dennis
Polyhedron 2013 Volume 52() pp:91-95
Publication Date(Web):22 March 2013
DOI:10.1016/j.poly.2012.11.019
Two salen type heteronuclear Cu–Gd complexes, namely, [(GdCuL1Cl3(CH3OH)2] (1) and [Gd2Cu4L24Cl2(OH)](PF6)3 (2) (H2L1 = N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,2-diaminocyclohexane and H2L2 = N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane) have been isolated. X-ray crystallographic analysis shows that 1 is of a typical neutral heterodinuclear Cu–Gd structure, while 2 features an unusual ionic hexanuclear Cu–Gd structure. Magnetic analysis reveals the dominant ferromagnetic interactions within the clusters.Graphical abstractWe present the syntheses, structure, and magnetic properties of two new Cu–Gd complexes based on salen-type ligands, including a hexanuclear compound that utilizes the PF6− counterion.Highlights► Ferromagnetic Gd–Cu dimer and hexamer clusters. ► Polynuclear cluster utilizing PF6− counter ions. ► Exact diagonalization for precise parameterization of magnetization.
Co-reporter:Yuxin Li, Pengfei Yan, Guangfeng Hou, Hongfeng Li, Peng Chen, Guangming Li
Journal of Organometallic Chemistry 2013 723() pp: 176-180
Publication Date(Web):
DOI:10.1016/j.jorganchem.2012.09.015
Co-reporter:Changwei Hong, Pengfei Yan, Qiang Li, Guangfeng Hou, Guangming Li
Journal of Organometallic Chemistry 2013 739() pp: 45-51
Publication Date(Web):
DOI:10.1016/j.jorganchem.2013.04.005
Co-reporter:Jingya Li ; Hongfeng Li ; Pengfei Yan ; Peng Chen ; Guangfeng Hou ;Guangming Li
Inorganic Chemistry 2012 Volume 51(Issue 9) pp:5050-5057
Publication Date(Web):April 20, 2012
DOI:10.1021/ic202473b
A new β-diketone, 2-(2,2,2-trifluoroethyl)-1-indone (TFI), which contains a trifluorinated alkyl group and a rigid indone group, has been designed and employed for the synthesis of two series of new TFI lanthanide complexes with a general formula [Ln(TFI)3L] [Ln = Eu, L = (H2O)2 (1), bpy (2), and phen (3); Ln = Sm, L = (H2O)2 (4), bpy (5), and phen (6); bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline]. X-ray crystallographic analysis reveals that complexes 1–6 are mononuclear, with the central Ln3+ ion eight-coordinated by six oxygen atoms furnished by three TFI ligands and two O/N atoms from ancillary ligand(s). The room-temperature photoluminescence (PL) spectra of complexes 1–6 show strong characteristic emissions of the corresponding Eu3+ and Sm3+ ions, and the substitution of the solvent molecules by bidentate nitrogen ligands essentially enhances the luminescence quantum yields and lifetimes of the complexes.
Co-reporter:Hong-Feng Li, Peng-Fei Yan, Peng Chen, Yan Wang, Hui Xu and Guang-Ming Li
Dalton Transactions 2012 vol. 41(Issue 3) pp:900-907
Publication Date(Web):16 Nov 2011
DOI:10.1039/C1DT11496D
A new bis-β-diketone, 3,3′-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln2(BTB)3(C2H5OH)2(H2O)2] [Ln = Eu (1), Gd (2)], [Ln2(BTB)3(DME)2] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu2(BTB)3(L)2] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1–7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3–7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu3+ complexes are determined and described.
Co-reporter:Fan Yang;Pengfei Yan;Quan Li;Peng Chen ;Guangming Li
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 27) pp:4287-4293
Publication Date(Web):
DOI:10.1002/ejic.201200357
Abstract
Two new Dy3 sandwich complexes, namely, [Dy3La3(CH3OH)2(NO3)3]·CH2Cl2·CH3OH·2H2O [1, H2La = N,N′-bis(salicylidene)-1,2-phenylenediamine] and [Dy3Lb3(OAc)3]·3CH3OH·H2O [2, H2Lb = N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine], have been synthesized from the reactions of a tetradentate salen-type ligand (H2La) with Dy(NO)3·6H2O and a hexadentate salen-type ligand (H2Lb) with Dy(OAc)3·6H2O. X-ray crystallographic analysis reveals that both 1 and 2 have a similar new triple-decker trinuclear sandwich structure. Magnetic studies indicate that 1 exhibits an antiferromagnetic interaction between the Dy3+ ions, whereas 2 exhibits a ferromagnetic interaction between spin carriers. Although both 1 and 2 display slow magnetic relaxation behavior, two relaxation processes were observed in 2, which expand on the recent reports of pure 4f-type single molecule magnets (SMMs).
Co-reporter:Peng Chen, Quan Li, Shuo Chen, Pengfei Yan, Yan Wang, Guangming Li
Inorganic Chemistry Communications 2012 Volume 17() pp:17-20
Publication Date(Web):March 2012
DOI:10.1016/j.inoche.2011.12.005
Reactions of 2-(2′-hydroxyphenyl)benzimidazole (HL) with Nd(NO3)3 ⋅ 6H2O and YbCl3 ⋅ 6H2O affords two lanthanide complexes [H2L]2[Nd(HL)2(NO3)4]2 ⋅ 2CH3OH ⋅ 2H2O (1) and [H2L][Yb(HL)2Cl4] ⋅ 2CH3OH (2), respectively. X-ray crystallographic analysis reveals that the two crystallographically distinct Nd3+ ions are ten-coordinated to two O atoms from two ligands and eight O atoms from four bidentate nitrate groups in 1. In the case of 2, the crystallographically distinct Yb3+ ion is hexa-coordinated to four Cl− ions and two O atoms in an octahedral geometry. Structural analysis indicates the importance of H-bondings and π–π stacking in the construction of 1 and 2. Complexes 1 and 2 exhibit essential NIR luminescence of Nd3+ and Yb3+ ions, respectively.Two unique 2-(2′-hydroxyphenyl)benzimidazole lanthanide complexes [H2L]2[Nd(HL)2(NO3)4]2 ⋅ 2CH3OH ⋅ 2H2O (1) and [H2L][Yb(HL)2Cl4] ⋅ 2CH3OH (2) have been isolated. The NIR luminescence of Nd3+ and Yb3+ ions for 1 and 2 are investigated, respectively.Highlights► Two 2-(2′-hydroxyphenyl)benzimidazole complexes have been prepared. ► Weak interaction dominates the structural construction. ► The ligand promotes the NIR luminescence of Nd3+ and Yb3+ ions.
Co-reporter:Ruiqiang Ding, Pengfei Yan, Guangfeng Hou, Peng Chen, Yan Wang, Guangming Li
Synthetic Metals 2012 Volume 162(21–22) pp:1894-1897
Publication Date(Web):December 2012
DOI:10.1016/j.synthmet.2012.07.024
A novel coordination polymer [Cd(4-tzbc)2]n (1) [H(4-tzbc) = 4-(1H-1,2,4-triazol-1-ylmethyl)benzoic acid] has been isolated by direct combination of unsymmetrical semi-rigid 4-tzbc with cadmium nitrate by the solvothermal method. Single-crystal X-ray diffraction study reveals that complex 1 exhibits a novel 3D rutile type framework with 1D channel. Thermal analysis suggests that 1 is of high thermostability at 345 °C. The photoluminescence of complex 1 reveals a cadmium ion disturbed ligand emission.Graphical abstractA novel coordination complex [Cd(4-tzbc)2]n with 3D rutile type topological structure containing unique 1D channel.Highlights► A novel complex [Cd(4-tzbc)2]n (1) with three-dimensional (3,6)-connected rutile type structure has been synthesized by solvothermal method. ► Thermal analysis suggests that complex 1 is of high thermostability at 345 °C. ► The photoluminescence of complex 1 reveals a cadmium ion disturbed ligand emission.
Co-reporter:Ting Gao, Li-Li Xu, Qian Zhang, Guang-Ming Li, Peng-Fei Yan
Inorganic Chemistry Communications 2012 Volume 26() pp:60-63
Publication Date(Web):December 2012
DOI:10.1016/j.inoche.2012.09.017
Two heteronuclear 3d–4f complexes obtained by salen-type ligand N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane (H2L1) and N,N′-bis(2-hydroxy-3-methoxy benzylidene)-1,2-diaminohexane (H2L2) have been isolated. They are co-crystallized complex [Yb(ZnL1)(OAc)2(H2O)]·[Yb(ZnL1)(OAc)3]·PF6·CH3OH (1), trinuclear complex [Sm(ZnL2)2Cl2(H2O)2]·PF6 (2). In complexes 1 and 2 the anion PF6 called counteranion is not only a role to neutralize overall charge in the solid but also to regulate frameworks. The complexes were structurally characterized by single crystal X-ray crystallographic studies and their photophysical properties were investigated.Two salen-type heteronuclear 3d–4f complexes were isolated and structurally characterized by single crystal X-ray crystallographic studies. In the two complexes, the anion PF6 called a counteranion has the roles of neutralizing the overall charge in a solid and regulating frameworks. Their photophysical properties were also investigated.Highlights► Heterometallic complexes Zn–Ln (Ln = Yb, Sm) assembled from salen-type ligand ► The polynuclear structure engineering by framework-regulator PF6 anions ► Enhancement of near-infrared and luminescent properties
Co-reporter:Bin-Qiu Liu, Peng-Fei Yan, Ju-Wen Zhang, Guang-Ming Li
Journal of Organometallic Chemistry 2012 710() pp: 80-85
Publication Date(Web):
DOI:10.1016/j.jorganchem.2012.03.009
Co-reporter:Peng-Fei Yan, Shuo Chen, Peng Chen, Ju-Wen Zhang and Guang-Ming Li
CrystEngComm 2011 vol. 13(Issue 1) pp:36-39
Publication Date(Web):26 Oct 2010
DOI:10.1039/C0CE00553C
Unique quadridentate salen type triple-decker dinuclear sandwich ytterbium complex [Yb2L3(CH3OH)]·0.5H2O (1) and triple-decker trinuclear sandwich ytterbium complex [Yb3L3(CH3OH)2(NO3)3]·CH3OH·5H2O (2) are isolated from the reactions of Yb(OAc)3·4H2O and Yb(NO3)3·6H2O with H2L, respectively (H2L = N,N′-bis(salicylidene)-1,2-(phenylene-diamine)). Complex 2 could be harvested from the addition of complex 1 and Yb(NO3)3·6H2O. Near infrared (NIR) lanthanide luminescence and the lifetime of complexes 1 and 2 are conducted and described.
Co-reporter:Peng Chen, Han Chen, Pengfei Yan, Yan Wang and Guangming Li
CrystEngComm 2011 vol. 13(Issue 20) pp:6237-6242
Publication Date(Web):19 Aug 2011
DOI:10.1039/C1CE05501A
Three types of phenolate oxygen-bridged N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-diaminophenylene 3d–4f heteronuclear and 4f tetranuclear complexes, namely, [(LZnCl)PrCl2(CH3OH)2]2 (1), [(LZnCl)LnCl(OAc)(CH3OH)] (Ln = Tb (2) and Dy (3)) and [{(LLu2)(OAc)2(H2O)(OH)}2(ZnCl4)]·2H2O (4) are obtained by reactions of H2L (H2L = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine), LnCl3·6H2O (Ln = Pr, Tb, Dy and Lu) and Zn(OAc)2·2H2O in CH3OH/CH2Cl2. X-Ray crystallographic analysis reveals that complex 4 possesses a novel defect-dicubane core, where four Lu3+ ions are inserted into the two sets of N2O2 and O2O2 cavities among the two tail-to-tail ligands. The structural investigations unambiguously testify that the lanthanide contraction and the rigid ligand cooperatively affect the formation of complexes 1–4, where Ln3+ ions with large, medium and small radius are composed in three different structures. The fluorescent spectrum of complex 2 exhibits the characteristic metal-centred fluorescence of Tb3+ ions.
Co-reporter:Ju-Wen Zhang, Peng-Fei Yan, Guang-Ming Li, Bin-Qiu Liu, Peng Chen
Journal of Organometallic Chemistry 2010 695(10–11) pp: 1493-1498
Publication Date(Web):
DOI:10.1016/j.jorganchem.2010.03.002
Co-reporter:Bin-Qiu Liu, Peng-Fei Yan, Ju-Wen Zhang, Peng Chen, Guang-Ming Li
Journal of Organometallic Chemistry 2010 695(22) pp: 2441-2446
Publication Date(Web):
DOI:10.1016/j.jorganchem.2010.07.010
Co-reporter:Yanping Dong, Pengfei Yan, Xiaoyan Zou, Xu Yao, Guangfeng Hou and Guangming Li
Dalton Transactions 2016 - vol. 45(Issue 22) pp:NaN9157-9157
Publication Date(Web):2016/04/29
DOI:10.1039/C6DT00442C
A series of four indole-derivative β-diketone mononuclear dysprosium complexes, namely, Dy(EIFD)3(bpy)·CH3CN (1), Dy(EIFD)3(phen)·CH2Cl2 (2), Dy(EIFD)3(dpq)·CH2Cl2 (3), and Dy(EIFD)3(dppz)·2H2O (4) (EIFD = 1-(1-ethyl-1H-indol-3-yl)-4,4,4-trifluorobutane-1,3-dione, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dpq = dipyrazine[2,3-f:2′,3′-h]quinoxaline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine) have been isolated by reactions of EIFD, DyCl3·6H2O and a series of auxiliary ligands. X-ray crystallographic analysis reveals that complexes 1–4 are all eight-coordinated mononuclear structures. Magnetic studies indicate that complexes 1–4 are all single-molecule magnets. Notably, the auxiliary ligands play an essential role in regulating their magnetism. The corresponding structural and magnetic parameters have been discussed in detail.
Co-reporter:Daniel M. Pajerowski, Quan Li, Jason Hyun, Cindi L. Dennis, Daniel Phelan, Pengfei Yan, Peng Chen and Guangming Li
Dalton Transactions 2014 - vol. 43(Issue 31) pp:NaN11980-11980
Publication Date(Web):2014/06/27
DOI:10.1039/C4DT01329H
Three chloride-bridged lanthanide compounds, [Ln4Cl6(CH3OH)12(OH)2]·4Cl·2CH3OH [Ln = Gd (1), Dy (2) and Er (3)], have been unexpectedly isolated by the reactions of LnCl3·6H2O and N,N′-bis(salicylidene)-1,2-(phenylene-diamine) (H2L). X-ray crystallographic analysis reveals a triclinic cell with a unique defect-dicubane {Ln4} core and the structure across this series is nominally isomorphic. Measurements of direct current magnetic susceptibility and isothermal magnetization give insight into the relevant cluster Hamiltonians for 1, 2, and 3, and alternating current susceptibility shows slow relaxation in 2, but not in 1 or 3 down to 2 K and up to 1 kHz.
Co-reporter:Yanping Dong, Pengfei Yan, Xiaoyan Zou, Tianqi Liu and Guangming Li
Journal of Materials Chemistry A 2015 - vol. 3(Issue 17) pp:NaN4415-4415
Publication Date(Web):2015/03/23
DOI:10.1039/C5TC00321K
A series of four β-diketone mononuclear dysprosium complexes, namely, Dy(EIFD)3(H2O)·CH2Cl2 (1), Dy(EIFD)3(DMF)·CH2Cl2 (2), Dy(EIFD)3(DMSO) (3), and Dy(EIFD)3(TPPO) (4) (EIFD: 1-(1-ethyl-1H-indol-3-yl)-4,4,4-trifluorobutane-1,3-dione, TPPO: triphenylphosphine oxide), have been isolated by the reactions of a newly designed β-diketone EIFD, DyCl3·6H2O and DMF, DMSO, TPPO, respectively. X-ray crystallographic analysis reveals that complexes 1–4 are isomorphic mononuclear structures in which the Dy(III) ion is rarely seven-coordinated with C3v geometry. Magnetic studies indicate that all complexes 1–4 are single-molecule magnets. The correlations between magnetism and the distortion of the coordination symmetry around the Dy(III) ions have been investigated. Notably, the quantum tunneling of magnetization (QTM), which universally exists in the lanthanide complexes, has been effectively suppressed in this system more related to the less deviation from the ideal C3v symmetry.
Co-reporter:Xiaoyan Zou, Mingjie Li, Pengfei Yan, Juwen Zhang, Guangfeng Hou and Guangming Li
Dalton Transactions 2013 - vol. 42(Issue 26) pp:NaN9489-9489
Publication Date(Web):2013/04/04
DOI:10.1039/C3DT50534K
Two types of N,N′-bis(salicylidene)-1,3-propanediamine (H2L) lanthanide complexes, viz. [Ln(NO3)3(H2L)2]·0.2CH3OH [Ln = La (1), Ce (2) and Pr (3)] and [Ln(NO3)3(H2L)2]2·CH2Cl2·CH3OH [Ln = Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Yb (9)], have been isolated by reactions of H2L with Ln(NO3)3·6H2O. X-ray crystallographic and PXRD analysis reveal that 1–3 are isomorphic possessing a novel one-dimensional (1D) ladder-like double-chain structure. Complexes 4–9 are isostructural exhibiting a discrete dinuclear structure. Luminescent analysis reveals the lanthanide ion and ligand-centered co-luminescence for 5, 6 and 8, which are attributed to the incomplete energy transfer from the triplet state of H2L to the resonance energy level of the corresponding Ln(III) ion. Further, the characteristic near infrared (NIR) luminescence of Nd(III) and Yb(III) ions for complexes 4 and 9 have been revealed.
Co-reporter:Hong-Feng Li, Peng-Fei Yan, Peng Chen, Yan Wang, Hui Xu and Guang-Ming Li
Dalton Transactions 2012 - vol. 41(Issue 3) pp:NaN907-907
Publication Date(Web):2011/11/16
DOI:10.1039/C1DT11496D
A new bis-β-diketone, 3,3′-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln2(BTB)3(C2H5OH)2(H2O)2] [Ln = Eu (1), Gd (2)], [Ln2(BTB)3(DME)2] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu2(BTB)3(L)2] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1–7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3–7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu3+ complexes are determined and described.
Co-reporter:Yanping Dong, Pengfei Yan, Xiaoyan Zou and Guangming Li
Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 9) pp:NaN836-836
Publication Date(Web):2015/06/24
DOI:10.1039/C5QI00079C
A series of four β-diketone mononuclear dysprosium complexes, namely, Dy(DBM)3(bpy) (1), Dy(DBM)3(phen)·Tol (2), Dy(DBM)3(dpq)·Tol (3), and Dy(DBM)3(dppz) (4) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, dpq = dipyrazine[2,3-f:2′,3′-h]quinoxaline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, Tol = toluene) have been isolated by the reactions of dibenzoylmethane (DBM), azacyclo-auxiliary ligands and DyCl3·6H2O. X-ray crystallographic analysis reveals that complexes 1–4 are all eight-coordinate mononuclear structures. The azacyclo-auxiliary ligands have a dramatic effect on the structure and magnetic characteristics of complexes 1–4, originating from the different degrees of deviation from the ideal coordination symmetries. Complexes 1 and 2 display a single relaxation mode under 0 Oe and complexes 3 and 4 display two single relaxation modes under 2000 Oe.
Co-reporter:Qiang Li, Pengfei Yan, Guangfeng Hou, Yan Wang and Guangming Li
Dalton Transactions 2013 - vol. 42(Issue 21) pp:NaN7815-7815
Publication Date(Web):2013/03/18
DOI:10.1039/C3DT50261A
Three new 7,7,8,8-tetracyanoquinodimethane (TCNQ) alkaline-earth metal complexes, namely {[M2(TCNQ)3(H2O)6]·TCNQ}n (M = Ca (1), Sr (2) and Ba (3)) have been synthesized by salt elimination reactions. X-ray crystallographic analysis reveals that complexes 1, 2 and 3 are isomorphic featuring a unique 3D structure. Cyclic and differential pulse voltammograms for complexes 1–3 show a reversible one-electron oxidation and a reversible one-electron reduction within the electrochemical window of CH3CN. Their electrochemical HOMO–LUMO gap and reversibility are examined.
Co-reporter:Jing-Wen Sun, Peng-Fei Yan, Guang-Hui An, Jing-Quan Sha, Cheng Wang and Guang-Ming Li
Dalton Transactions 2016 - vol. 45(Issue 4) pp:NaN1667-1667
Publication Date(Web):2015/12/08
DOI:10.1039/C5DT04094A
To investigate the influence of POM species, temperature and counterions on the structures of POM-MOFs containing Cu-tda second building units (SBUs), six new complexes with various dimensionalities, e.g. three dimensional (3D) [Cu(H2tda)(H2O)2]4[SiW12O40]·12H2O (1), two dimensional (2D) [Cu2(H2tda)2(H2O)3]·[Cu(H2tda)(H2O)2]·[PMo12O40]·5H2O (2), H-bond 2D [Cu(H2tda)(H2O)2]3·[PMo12O40]·[Cu(Htda)(H2O)3]·8H2O (3), one dimensional (1D) [Cu2(H2tda)2(H2O)4]2·[Cu2(tda)2(H2O)4]·[HPW12O40]·5H2O (4), 1D [Cu2(H2tda)2(H2O)4][SiW12O40]·(TMA)2·3H2O (5), and zero dimensional (0D) [Cu(H2tda)(H2O)3][SiW12O40]·(TMA)3·H2O (6), were isolated depending on the reaction conditions. It is observed that the POM species, temperature and counterions exhibit an essential effect on the structures, which results in the formation of various dimensional POM-MOF complexes 1–6. In addition, photocatalytic degradation of RhB by complexes 1, 5 and 6 under UV irradiation was also investigated.
Co-reporter:Chang Feng, Jing-Wen Sun, Peng-Fei Yan, Yu-Xin Li, Tian-Qi Liu, Qing-Yan Sun and Guang-Ming Li
Dalton Transactions 2015 - vol. 44(Issue 10) pp:NaN4647-4647
Publication Date(Web):2015/01/19
DOI:10.1039/C4DT03457K
A series of L-di-2-thenoyltartaric acid lanthanide coordination polymers, namely, {[La2L3(CH3OH)6(H2O)]·CH3OH·H2O}n (1), {[Ln2L3(CH3OH)x(H2O)6−x]·aCH3OH·bH2O}n, [Ln = Eu (2), x = 2, a = 0.5, b = 0.25; Ln = Gd (3), x = 3, a = 1, b = 0; Ln = Tb (4), x = 2, a = 1, b = 0], {[(Eu0.037Tb0.963)2L3(CH3OH)2(H2O)4]·CH3OH·2.75H2O}n (5), {[(Eu0.051Tb0.406La0.543)2L3(CH3OH)2(H2O)4]·0.5CH3OH·2H2O}n (6), and {[(Eu0.068Tb0.363Gd0.569)2L3(CH3OH)3(H2O)3]·CH3OH·H2O}n (7), have been synthesized using facile reactions of H2L (H2L = L-di-2-thenoyltartaric acid) with LnCl3·6H2O under ambient temperature. X-ray crystallographic analysis reveals that complexes 1–4 are isostructural, featuring one-dimensional (1D) ladder-like chain structures, in which the Ln3+ ions are bridged by the carboxylate groups of the ligands. The luminescent spectra in the solid state at room temperature reveal that complexes 2 and 4 exhibit the characteristic red and green luminescence of Eu3+ and Tb3+ ions, respectively, whereas complexes 1 and 3 display the blue emission of the ligand with a broad band centered at 422 nm. Notably, the mixed-lanthanide coordination polymers 5–7 exhibit color-tunable luminescence from yellow and white to blue upon variation of the excitation wavelength. It realizes color-tunable and white-light emission in 1D carboxylic acid mixed-lanthanide coordination polymers.
Co-reporter:Fang Luan, Pengfei Yan, Jing Zhu, Tianqi Liu, Xiaoyan Zou and Guangming Li
Dalton Transactions 2015 - vol. 44(Issue 9) pp:NaN4053-4053
Publication Date(Web):2015/01/09
DOI:10.1039/C4DT02607A
Four isomorphic tetranuclear lanthanide complexes, namely [Ln4(L)2(HL)2(NO3)2(OH)2](NO3)2·4H2O (Ln = Dy (1); Tb (2); Ho (3); Er (4)), constructed using hexadentate salen-type ligand N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine, have been isolated. X-ray crystallographic analysis reveals that all of the complexes 1–4 are of discrete tetranuclear structure with a unique {Ln4O8} core in which four lanthanide ions are coplanar in a rhombic frame. There are two crystallographically unequivalent lanthanide ions, that is the Ln1III ion which is nine-coordinated in a monocapped square-antiprismatic geometry of the C4v point group and the Ln2III ion which is eight-coordinated in a distorted bicapped trigonal-prismatic geometry of the C2v point group. Magnetic analysis reveals that complex 1 exhibits two slow magnetic relaxations with the highest energy barrier among the reported tetranuclear salen-type dysprosium SMMs. This further extends the available SMMs of salen-type lanthanide complexes.
Co-reporter:Fengming Zhang, Pengfei Yan, Hongfeng Li, Xiaoyan Zou, Guangfeng Hou and Guangming Li
Dalton Transactions 2014 - vol. 43(Issue 33) pp:NaN12581-12581
Publication Date(Web):2014/05/22
DOI:10.1039/C4DT00837E
A series of pyrazine-2,3,5,6-tetracarboxylate alkali–lanthanide coordination frameworks, namely [NaLn(pztc)(H2O)3]·H2O [Ln = Ce (1), Sm (2), Eu (3), Gd (4) and Tb (5); H4pztc = pyrazine-2,3,5,6-tetracarboxylic acid], have been synthesized by reacting Ln(NO3)3·6H2O with H4pztc in the presence of NaOH at room temperature. X-ray crystallographic analysis reveals that complexes 1–5 are isostructural, featuring three-dimensional (3D) networks with a unique (411·68·82)(43·62·8)(43) topology in which the ligand displays a novel μ7-coordination mode. The photoluminescence (PL) spectra in the solid state reveal that complexes 2, 3 and 5 exhibit the characteristic luminescence of Sm(III), Eu(III) and Tb(III) ions, respectively, while complex 4 displays a broad band in the range of 400–650 nm (λmax = 505 nm) which exhibits about 103 nm red-shift and enhancement compared to the band of the free ligand. Further, the isostructural two-component Eu(III)-doped Gd(III) complexes realize color-tunable luminescence from red to yellow, white, green and blue by the variation of excitation wavelengths. They represent the first example of full-color-tunable emission in lanthanide coordination frameworks by the variation of excitation light.
Co-reporter:Xiaoyan Zou, Pengfei Yan, Juwen Zhang, Fengming Zhang, Guangfeng Hou and Guangming Li
Dalton Transactions 2013 - vol. 42(Issue 36) pp:NaN13199-13199
Publication Date(Web):2013/06/21
DOI:10.1039/C3DT51556G
A series of five N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-propanediamine (H2L) ytterbium complexes, namely, [Yb(H2L)2(CH3OH)](ClO4)3 (1), [Yb(H2L)(NO3)3]2·CH2Cl2 (2), [Yb(H2L)2(NO3)]2(PF6)4·4H2O·2CH2Cl2 (3), [Yb(H2L)(OAc)2]2(PF6)2·4CH2Cl2 (4) and [Yb3L′3(OH)2Cl(H2O)5]Cl3·4H2O (5) (HL′ = 2-hydroxy-3-methoxybenzaldehyde), have been synthesized by reactions of H2L with multifarious Yb(III) salts. X-ray diffraction analysis reveals that complex 1 shows a unique mononuclear structure constructed from two chelating H2L ligands in crossover mode. Complex 2 exhibits a dinuclear structure bridged by two H2L ligands. Complexes 3 and 4 possess two novel dinuclear structures linked by NO3− and OAc− anions, respectively. Complex 5 displays a trinuclear structure supported by three L′ and two OH− anions. Noticeable, complex 3 can be transformed from 2 by introducing (NH4)(PF6). The PF6− counterion plays an essential role in steering the structural transformation. The anions dominate the final structures of 1–5. All complexes 1–5 exhibit NIR luminescence, which can be rationalized on the basis of different structural effects. Preliminary catalytic studies reveal that all complexes 1–5 are able to catalyze effectively a typical Henry reaction with good yields.
Co-reporter:Weizuo Li, Pengfei Yan, Guangfeng Hou, Hongfeng Li and Guangming Li
Dalton Transactions 2013 - vol. 42(Issue 32) pp:NaN11547-11547
Publication Date(Web):2013/05/30
DOI:10.1039/C3DT50580D
A new β-diketone, 5,6-dimethoxy-2(2,2,2-trifluoroethyl)-1-indone (5,6-DTFI), has been designed and synthesized. Two series of four 5,6-DTFI Sm3+ and Eu3+ complexes, namely, Eu(5,6-DTFI)3(H2O)2 (1), Eu(5,6-DTFI)3(Phen) (2), Sm(5,6-DTFI)3(H2O)2 (3) and Sm(5,6-DTFI)3(Phen) (4) (Phen = 1,10-phenanthroline), have been isolated. X-ray diffraction analysis reveals that all complexes 1–4 are of mononuclear structures. Luminescent and phosphorescent spectra of complexes 1–4 show strong characteristic emissions of the corresponding Eu3+ and Sm3+ ions. Upon complexes 1 and 2 were doped into the poly(methylmethacrylate) (PMMA) forming the films, the PMMA polymer matrix acting as a co-sensitizer for Eu3+ ion enhances the luminescent lifetimes, overall quantum yields and the thermal stability in comparison with the precursor complexes.
![Phenol, 2,2'-[1,3-propanediylbis(nitrilomethylidyne)]bis[6-methoxy-](/data/chemimg/89800/5767-53-3.png)
![Phenol, 2,2'-[1,3-propanediylbis(nitrilomethylidyne)]bis[6-methoxy-](/data/chemimg/89800/5767-53-3_b.png)
