Co-reporter:Juan Feng;Cheng-Yong Su;Haobin Fang;Zhenguo Chi;Lihua Zeng;Kunyu Chen
Langmuir November 22, 2016 Volume 32(Issue 46) pp:12184-12189
Publication Date(Web):2017-2-22
DOI:10.1021/acs.langmuir.6b03678
Supramolecular gels with hierarchical order and complexity have been assembled. The gels contain well-defined Ag4L2 luminescent supramolecular cages as cores, which are cross-linked via Ag–P coordination bonding. The resulting gels are highly luminescent and exhibit rich stimuli-responsive behaviors toward mechanical and chemical (nitroexplosive and anions) stimuli. The gels could be transformed to highly luminescent crystal materials upon addition of halogen anions, in which only traces of lumiphor are accommodated in a host crystal matrix.
Co-reporter:Xiying Feng;Lihua Zeng;Dianting Zou;Zizhe Zhang;Guihao Zhong;Shuyin Peng;Liping Liu;Liuping Chen
RSC Advances (2011-Present) 2017 vol. 7(Issue 59) pp:37194-37199
Publication Date(Web):2017/07/24
DOI:10.1039/C7RA05783K
A novel approach has been proposed to fabricate MOF-based luminescent gel materials with trace amounts of doping in order to study the role of trace defects in metal–organic gel materials. UiO-66-based ZrBDC (BDC = 1,4-benzene dicarboxylate) gels were first prepared from Zr4+ and H2BDC under mild conditions, and subsequently trace doping (as low as 0.01 mol%) of the ZrBDC gel materials with H4TCPE (tetrakis(4-carboxyphenyl)ethylene) was achieved successfully. The resulting ZrBDC–TCPE0.01% gel material features mild synthetic conditions and retains the high porosity of parent UiO-66 gel materials. Moreover, trace doping causes a remarkable change to the luminescence properties and the gel emits blue luminescence with high quantum yield (59%). ZrBDC–TCPE0.01% shows responses with high sensitivity and selectivity for nitroaromatics (picric acid) in the aqueous phase and detects picric acid as low as parts per billion (24 ppb). The present luminescent gel materials provide new insights into developing functional metal–organic materials through trace defects, which may remarkably alter the properties of metal–organic materials.
Co-reporter:Lihua Zeng, Peisen Liao, Haoliang Liu, Liping Liu, Ziwei Liang, Jianyong Zhang, Liuping Chen and Cheng-Yong Su
Journal of Materials Chemistry A 2016 vol. 4(Issue 21) pp:8328-8336
Publication Date(Web):26 Apr 2016
DOI:10.1039/C6TA01035K
A series of (metallo)porphyrin imine gels have been synthesized based on imine chemistry. The resulting aerogels have sponge-like porous networked structures consisting of interconnected nanoparticles with hierarchical porosity. The aerogels have high specific surface areas (up to 719 m2 g−1) and large pore volumes (up to 2.60 cm3 g−1). The effect of metal ions on the uptake of gases in these aerogels was investigated. The impregnation of various metal ions (Pd(II), Ni(II), Mn(III), Fe(III) and Sn(IV)) enhances the uptake capacity of various gases (e.g., CO2) despite their higher densities. Among the metal ions, Pd(II) is the best to increase the adsorption capacity and the isosteric heat of CO2 adsorption. The Pd-tapp–A4 aerogel exhibits CO2 volumetric uptake (1.62 mmol g−1, 7.13 wt% at 298 K, 1 bar) with a high isosteric heat of adsorption (40.0 kJ mol−1). The gels also show potential applications in catalysis because of their unique hierarchical porosity and the availability of metal centers. In combination with microfluidic technology, a catalytic gel capillary reactor has been assembled with the Pd-tapp–A4 gel supported on the inner surface of a functionalized capillary.
Co-reporter:Juan Feng, Liu Yao, Jianyong Zhang, Yingxiao Mu, Zhenguo Chi and Cheng-Yong Su
Dalton Transactions 2016 vol. 45(Issue 4) pp:1668-1673
Publication Date(Web):14 Dec 2015
DOI:10.1039/C5DT04319K
A novel phosphine-based tetragonal Ag4L2 cage has been assembled from a tetraphenylethylene (TPE)-based tetraphosphine and Ag+ ions. The cage structure is maintained both in solutions and in the solid state. Ag4L2 emits strong fluorescence not only in dilute solutions but also in aggregated states. The turn-on fluorescence of TPE-P4 in dilute solutions is attributed to the formation of Ag4L2. Ag4L2 shows potential as a fluorescent sensor towards anions and olefin compounds, which arises from binding of the guest anions/olefin compounds by its labile silver centres.
Co-reporter:Liping Liu; Jianyong Zhang;Haobin Fang; Liuping Chen ; Cheng-Yong Su
Chemistry – An Asian Journal 2016 Volume 11( Issue 16) pp:2278-2283
Publication Date(Web):
DOI:10.1002/asia.201600698
Abstract
Metal–organic frameworks (MOFs) including the UiO-66 series show potential application in the adsorption and conversion of CO2. Herein, we report the first tetravalent metal-based metal–organic gels constructed from ZrIV and 2-aminoterephthalic acid (H2BDC-NH2). The ZrBDC-NH2 gel materials are based on UiO-66-NH2 nanoparticles and were easily prepared under mild conditions (80 °C for 4.5 h). The ZrBDC-NH2-1:1-0.2 gel material has a high surface area (up to 1040 m2 g−1) and showed outstanding performance in CO2 adsorption (by using the dried material) and conversion (by using the wet gel) arising from the combined advantages of the gel and the UiO-66-NH2 MOF. The ZrBDC-NH2-1:1-0.2 dried material showed 38 % higher capture capacity for CO2 at 298 K than microcrystalline UiO-66-NH2. It showed high ideal adsorbed solution theory selectivity (71.6 at 298 K) for a CO2/N2 gas mixture (molar ratio 15:85). Furthermore, the ZrBDC-NH2-1:1-0.2 gel showed activity as a heterogeneous catalyst in the chemical fixation of CO2 and an excellent catalytic performance was achieved for the cycloaddition of atmospheric pressure of CO2 to epoxides at 373 K. In addition, the gel catalyst could be reused over multiple cycles with no considerable loss of catalytic activity.
Co-reporter:Haoliang Liu, Juan Feng, Jianyong Zhang, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Science 2015 vol. 6(Issue 4) pp:2292-2296
Publication Date(Web):18 Feb 2015
DOI:10.1039/C5SC00314H
A novel dynamic covalent gel strategy is reported to immobilize an asymmetric catalyst within the channels of a microfluidic flow reactor. A layer of a catalytically active Mn–salen dynamic covalent imine gel matrix was coated onto a functionalized capillary. Mn–salen active moiety was incorporated into dynamic covalent imine gel matrix via the reaction of a chiral Mn–salen dialdehyde unit with a tetraamine linker. The catalytic activity of the capillary reactor has been demonstrated in enantioselective kinetic resolution of secondary alcohols.
Co-reporter:Jianyong Zhang, Liping Liu, Haoliang Liu, Minjuan Lin, Siyan Li, Gangfeng Ouyang, Liuping Chen and Cheng-Yong Su
Journal of Materials Chemistry A 2015 vol. 3(Issue 20) pp:10990-10998
Publication Date(Web):14 Apr 2015
DOI:10.1039/C5TA00557D
A series of novel aerogels have been obtained based on imine chemistry. The aerogels were prepared by polycondensation of various bridging aldehydes and amines via a sol–gel process. The imine aerogels of tetrakis-(4-aminophenyl)methane (A1) consist of three-dimensional networks of interconnected nanometer-sized particles with hierarchically porous structures. The porosity of the areogels is tuneable by the choice of precursors, precursor concentration and reaction solvent. The aerogels exhibit BET surface areas up to 1021 m2 g−1 (A1-biformyl aerogel A1B1-0.030), as measured by N2 adsorption at 77 K. The A1B1-0.030 aerogel possesses a CO2 uptake of 1.5 mmol g−1 at 298 K and 1.0 bar with an isosteric heat of 38.1 kJ mol−1 and displays high CO2/N2 selectivity up to 70.9, which is derived from the ideal adsorbed solution theory. The A1B1-0.030 aerogel also shows a good capacity to uptake aromatic toluene molecules from an aqueous solution. Moreover, the hierarchically porous structure endows the A1B1-0.030 aerogel with good performance in enrichment of large molecules (polycyclic aromatic hydrocarbons PAHs and organochlorine pesticides OCPs) as the coating adsorbent in solid-phase microextraction (SPME) fibres.
Co-reporter:Hongmiao Li;Xin Tan
Chinese Journal of Chemistry 2015 Volume 33( Issue 1) pp:141-146
Publication Date(Web):
DOI:10.1002/cjoc.201400479
Abstract
Incorporation of phosphine-Pd catalytic centers in gel network is an important strategy to develop highly active catalysts. In this contribution we show that catalytically active phosphine-Pd(II) gels can be readily obtained via reaction of rigid bridging terpyridyl phosphines and Pd(II). The terpyridyl phosphines, Py2P2 and Py2P, contain one 4,2′:6′,4′ ′-terpyridyl group and two/one diphenylphosphino groups. Reactions of Py2P2/Py2P and Pd(II) in CHCl3-MeOH afforded the corresponding phosphine-Pd(II) gels at room temperature or at elevated temperature (40°C). The gelation is driven by formation of metal-organic coordination. Mild heating is important in triggering the formation of Py2P-Pd(II) gel. The gels have a coherent, rigid spongy porous network of continuous nanometer-sized particles. The phosphine-Pd(II) gels showed high activity in the Suzuki-Miyaura reactions of aryl bromides under ambient conditions and could be recycled and reused.
Co-reporter:Shi-Chao Wei;Dr. Mei Pan;Yuan-Zhong Fan;Haoliang Liu; Jianyong Zhang; Cheng-Yong Su
Chemistry - A European Journal 2015 Volume 21( Issue 20) pp:7418-7427
Publication Date(Web):
DOI:10.1002/chem.201406517
Abstract
Creating cavities in varying levels, from molecular containers to macroscopic materials of porosity, have long been motivated for biomimetic or practical applications. Herein, we report an assembly approach to multiresponsive supramolecular gels by integrating photochromic metal–organic cages as predefined building units into the supramolecular gel skeleton, providing a new approach to create cavities in gels. Formation of discrete O-Pd2L4 cages is driven by coordination between Pd2+ and a photochromic dithienylethene bispyridine ligand (O-PyFDTE). In the presence of suitable solvents (DMSO or MeCN/DMSO), the O-Pd2L4 cage molecules aggregate to form nanoparticles, which are further interconnected through supramolecular interactions to form a three-dimensional (3D) gel matrix to trap a large amount of solvent molecules. Light-induced phase and structural transformations readily occur owing to the reversible photochromic open-ring/closed-ring isomeric conversion of the cage units upon UV/visible light radiation. Furthermore, such Pd2L4 cage-based gels show multiple reversible gel–solution transitions when thermal-, photo-, or mechanical stimuli are applied. Such supramolecular gels consisting of porous molecules may be developed as a new type of porous materials with different features from porous solids.
Co-reporter:Shi-Chao Wei;Dr. Mei Pan;Yuan-Zhong Fan;Haoliang Liu; Jianyong Zhang; Cheng-Yong Su
Chemistry - A European Journal 2015 Volume 21( Issue 20) pp:
Publication Date(Web):
DOI:10.1002/chem.201582062
Co-reporter:Shi-Chao Wei;Mei Pan;, Kang Li;Sujuan Wang;Cheng-Yong Su
Advanced Materials 2014 Volume 26( Issue 13) pp:2072-2077
Publication Date(Web):
DOI:10.1002/adma.201304404
Co-reporter:Weijun Luo, Yixuan Zhu, Jianyong Zhang, Jiajun He, Zhenguo Chi, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Communications 2014 vol. 50(Issue 80) pp:11942-11945
Publication Date(Web):14 Aug 2014
DOI:10.1039/C4CC05120C
A novel dynamic covalent gel has been prepared via the imine bond formation reaction of tetraamine building blocks with luminescent tetraphenylethene tetraaldehyde units. The gel shows high hierarchical porosity (SBET = 512 m2 g−1) and remarkable aggregation-induced emission enhancement, which has been demonstrated to be a selective sensor.
Co-reporter:Jianyong Zhang, Qiuli Yang, Yixuan Zhu, Haoliang Liu, Zhenguo Chi and Cheng-Yong Su
Dalton Transactions 2014 vol. 43(Issue 42) pp:15785-15790
Publication Date(Web):18 Aug 2014
DOI:10.1039/C4DT01808G
A tetraphenylethylene-based phosphine, 1,1,2,2-tetrakis((4-diphenylphosphino)phenyl)ethylene (TPE-P4), was synthesized and showed novel aggregation-induced and mechano-responsive emission. A mixture of TPE-P4 and Ag+ could fix atmospheric CO2in situ as carbonate ions in neutral solution to yield a rare 3D metal–organic framework with zeolite-like SOD topology, [Ag2(TPE-P4)CO3]x⊃nH2O (Ag-TPE-P4). Ag-TPE-P4 showed turn-on luminescence of TPE-P4, emitting bright bluish green light in the solid state.
Co-reporter:Minjuan Lin, Haoliang Liu, Philip W. Miller, Jianyong Zhang and Cheng-Yong Su
New Journal of Chemistry 2014 vol. 38(Issue 8) pp:3755-3761
Publication Date(Web):29 May 2014
DOI:10.1039/C4NJ00445K
Post-modification of supramolecular assemblies via covalent capture is an important strategy for the fabrication of functional materials. This paper describes the synthesis of supramolecular nanotubes with appended pyridyl groups based on N,N′,N′′-tris(3-methylpyridyl)trimesic amide (TMPTA), and their successful post-modification by 1,4-bis(bromomethyl)benzene. The original tubular morphology of the TMPTA nanotubes was found to stay intact following the modification process. The modified nanotubes are resistant to attack by strong acids and bases. The continuous network of covalent bonds throughout the tubular network is responsible for this stability. The formation of pyridinium cations upon modification results in positively charged surfaces of nanotubes that were found to be highly effective adsorbents for a range of anionic dyes, demonstrating both high adsorption capacity and selectivities over cationic and neutral dye species. These materials can be reused for dye capture without losses in their capture ability.
Co-reporter:Qiuli Yang, Xin Tan, Sujuan Wang, Jianyong Zhang, Liuping Chen, Jie-Peng Zhang, Cheng-Yong Su
Microporous and Mesoporous Materials 2014 Volume 187() pp:108-113
Publication Date(Web):15 March 2014
DOI:10.1016/j.micromeso.2013.12.025
•Organic–inorganic hybrid aerogels with high micro- and mesoporosity were prepared from Al(acac)3/Cr(acac)3 subunits.•Heterometallic aerogels were prepared.•The aerogels have relatively hydrophobic pore surface.•The aerogels show ability to absorb various guest molecules.Organic–inorganic hybrid aerogels are receiving growing attention due to their high tuneability. In this contribution a novel type of organic–inorganic hybrid aerogels with high micro- and mesoporosity have been prepared successfully from a bridging bis(acetylacetonate) ligand, 3,4-diacetyl-2,5-dioxohexane, and trivalent metal ions (Al3+ and Cr3+). The metal-acetylacetonate aerogels compose of nanoscale metal-organic particles, which aggregate to form the gel matrix. N2 sorption shows that the aerogels have high BET surface areas up to ∼1100 m2 g−1 and hierarchical porosity. The porosity can be altered by introducing of second divalent metal ions into the aerogel. The aerogels show ability to adsorb various gases (H2, CO2 and CH4) and vapors (MeOH and EtOH). Water sorption measurements reveal that the aerogels have relatively hydrophobic pore surface.Graphical abstract
Co-reporter:Minjuan Lin, Sujuan Wang, Jianyong Zhang, Weijun Luo, Haoliang Liu, Wei Wang, Cheng-Yong Su
Journal of Molecular Catalysis A: Chemical 2014 Volume 394() pp:33-39
Publication Date(Web):15 November 2014
DOI:10.1016/j.molcata.2014.06.039
•A porous imidazolium polymeric network has been prepared.•Its complexation with palladium yielded a Pd-NHC porous polymeric network.•The Pd-NHC network showed ability to absorb both hydrophilic and aromatic guests.•The Pd-NHC network catalyzed carbon–carbon coupling reactions in a heterogeneous way with excellent recyclability.A porous imidazolium polymeric network was synthesized via alkylation of tetrakis-[4-(1H-imidazole-1-yl)phenyl]methane with 1,4-bis(bromomethyl)benzene. Its complexation with palladium yielded a Pd-NHC porous polymeric network, namely Pd-pNHC. Pd-pNHC showed selective uptake of CO2 over N2 due to its polar surface. Pd-pNHC has a BET specific surface area of 308 m2 g−1 and a micropore volume of 0.190 cm3 g−1. Pd-pNHC showed ability to absorb both hydrophilic and aromatic guests (MeOH, EtOH and benzene). Pd(II) catalytically active centers within the porous polymeric network were readily accessible to substrates as demonstrated in Suzuki–Miyaura coupling reactions. High yields were achieved in the coupling reactions of various arylbromides under mild conditions. Additionally, Pd-pNHC catalyzed the reactions in a heterogeneous way and the catalyst could be used for at least ten times without loss of activity.
Co-reporter:Jianyong Zhang, Cheng-Yong Su
Coordination Chemistry Reviews 2013 Volume 257(7–8) pp:1373-1408
Publication Date(Web):April 2013
DOI:10.1016/j.ccr.2013.01.005
The design of metallogelators and incorporation of metals into supramolecular gels have received growing attention. Design strategies have been developed based on organogelators, including the incorporation of metal into low molecular weight organogelators (LMWGs), and coordination polymers assisted by auxiliary moieties (including lipophilic and hydrogen-bonding groups) as gelators. Additionally, a novel class of metal-organic gels lacking auxiliary moieties has recently been developed; these coordination-directed (induced) gels display novel properties e.g., in adsorption and catalysis and as templates for porous materials. This review highlights the design and properties of a diverse range of metallogelator types.Graphical abstractHighlights► Two general classes of metallogels developed including molecular metallogels and coordination polymer gels. ► Coordination polymer gelators developed assisted by auxiliary moieties. ► Metal-organic gelators developed lacking auxiliary moieties. ► Metal-organic gels with novel properties in adsorption, catalysis and as templates for porous materials.
Co-reporter:Sujuan Wang, Qiuli Yang, Jianyong Zhang, Xuepeng Zhang, Cunyuan Zhao, Long Jiang, and Cheng-Yong Su
Inorganic Chemistry 2013 Volume 52(Issue 8) pp:4198-4204
Publication Date(Web):March 26, 2013
DOI:10.1021/ic301781n
A charge-separated metal–organic framework (MOF) has been successfully synthesized from an imidazolium tricarboxylate ligand, N-(3,5-dicarboxylphenyl)-N′-(4-carboxylbenzyl)imidazolium chloride (DCPCBImH3Cl), and a zinc(II) dimeric secondary building unit, namely, DCPCBim-MOF-Zn, which shows an unprecedented 3,6-connected two-dimensional net topology with the point (Schläfli) symbol (42.6)2(44.69.82). The framework contains one-dimensional highly polar channels, and density functional theory calculations show that positive charges are located on the imidazolium/phenyl rings and negative charges on the carboxylate moieties. The charge-separated nature of the pore surface has a profound effect in their adsorption behavior, resulting in remarkable hysteretic sorption of various gases and vapors. For CO2, the hysteretic sorption was observed to occur even up to 298 K. Additionally, trace chloride anions present in the pore channels are able to modulate the gas-sorption behavior.
Co-reporter:Hongmiao Li, Yixuan Zhu, Jianyong Zhang, Zhenguo Chi, Liuping Chen and Cheng-Yong Su
RSC Advances 2013 vol. 3(Issue 37) pp:16340-16344
Publication Date(Web):17 Jul 2013
DOI:10.1039/C3RA40363G
To develop luminescent gels, a series of metal–organic gels have been successfully synthesised based on trivalent metal ions (Al3+, Cr3+, Fe3+, Ga3+, and In3+) and tetrakis(4-carboxyphenyl)ethylene (H4TCPE) that has aggregation-induced emission (AIE) features. Among these gels, the Al-TCPE gel has both high hierarchical micro- and mesoporosity and AIE effect. The Al-TCPE aerogel consists of metal–organic framework nanocomponents as revealed by TEM and PXRD, which contribute to its high microporosity. Using tetraphenylethylene as a building block endows the Al-TCPE gel with AIE photoluminescence. The Al-TCPE gel shows potential in the selective detection of explosives with picric acid chosen as a model explosive.
Co-reporter:Xin Tan, Lei Li, Jianyong Zhang, Xiaorui Han, Long Jiang, Fuwei Li, and Cheng-Yong Su
Chemistry of Materials 2012 Volume 24(Issue 3) pp:480
Publication Date(Web):December 13, 2011
DOI:10.1021/cm202608f
Metal–organic frameworks (MOFs) with phosphine based ligands are extremely attractive for catalysis. In this paper, phosphine has been successfully incorporated for the first time into three-dimensional (3D) MOFs. The MOFs are based on rigid L2M2 dimeric secondary building blocks assembled from Cu(I) and a pyridyl diphosphine ligand, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine, with Br– (CuL-Br), Cl– (CuL-Br), or PF6– (CuL-PF6) as counteranions. The structures have a 4.122 net topology, which can be further simplified to 64.82-qtz. The MOFs contain 1D homochiral channels. The PF6– anions hosted in the 1D channel of CuL-PF6 can be readily exchanged with Br– or Cl– while keeping the framework intact. The materials show anion-tunable flexible porosity. CuL-Br reveals gradual uptake of MeOH, while CuL-PF6 exhibits stepwise sorption for MeOH. The heterogeneous Lewis acid catalytic activity of the MOFs has been shown in ketalization reaction. CuL-Br and CuL-PF6 are active in the reactions between ethylene glycol and 2-butanone/cyclohexanone, up to 93% yield with 0.2 mol % catalyst loading. In contrast, no reaction happens between ethylene glycol and bulky benzophenone, suggesting profound size selectivity. The catalysts can be reused with the framework left intact for three runs without loss of activity.Keywords: catalysis; copper; metal−organic framework; phosphine; sorption;
Co-reporter:Shenglin Xiang, Lei Li, Jianyong Zhang, Xin Tan, Huanan Cui, Jianying Shi, Yuling Hu, Liuping Chen, Cheng-Yong Su and Stuart L. James
Journal of Materials Chemistry A 2012 vol. 22(Issue 5) pp:1862-1867
Publication Date(Web):05 Dec 2011
DOI:10.1039/C1JM14618A
A general method to prepare organic–inorganic hybrid aerogels has been presented. A series of organic–inorganic hybrid aerogels were successfully produced from 3d trivalent transition metals (Cr3+, Fe3+) and bridging carboxylic acids. Gelation of the Cr(III) gels was achieved by heating the precursor solution to temperatures above 80 °C, which is in sharp contrast to usual supramolecular gels. Among a range of ligands used, highly porous aerogels could be prepared from rigid carboxylate, e.g.1,4-benzenedicarboxylate and 1,3,5-benzenetricarboxylate. The porous aerogels can be described as a coherent, rigid spongy network of continuous nanometre-sized particles, which is significantly different from the usual fibrous network of supramolecular gels. The aerogels have tunable porous structures with micro- and mesoporosity depending on their reactant concentrations. Their surface areas, pore volumes, and average pore sizes were analysed by using nitrogen sorption, and the accessibility of the pores to bulky molecules was also evaluated. It represents a strategy to prepare hybrid materials with large porosity utilising structurally simple building blocks as precursors.
Co-reporter:Xin Tan, Jixian Zhan, Jianyong Zhang, Long Jiang, Mei Pan and Cheng-Yong Su
CrystEngComm 2012 vol. 14(Issue 1) pp:63-66
Publication Date(Web):03 Nov 2011
DOI:10.1039/C1CE05995E
Three-dimensional chiral (10,3)-c MOFs are generated via symmetry breaking from achiral precursors, 5-(pyridine-3-yl)isophthalic acid and M2+ (M = Cd, Zn, Mn), and chiral transmission from molecular axially chiral conformations to framework chirality is established.
Co-reporter:Xin Tan, Xue Chen, Jianyong Zhang and Cheng-Yong Su
Dalton Transactions 2012 vol. 41(Issue 13) pp:3616-3619
Publication Date(Web):09 Feb 2012
DOI:10.1039/C2DT00035K
Rigid bridging terpyridyl phosphine and AgOTf form nanofibres to induce gelation of organic solvents, and the gel emits blue luminescence by suppressing π–π interactions between ligands.
Co-reporter:Jin-Ji Wu, Man-Li Cao, Jian-Yong Zhang and Bao-Hui Ye
RSC Advances 2012 vol. 2(Issue 33) pp:12718-12723
Publication Date(Web):23 Oct 2012
DOI:10.1039/C2RA22549B
A stable nanocomposite metallogel was obtained by the addition of [Na(L)(H2O)]·2H2O (HL = 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol) to an aqueous solution of Cu2(OAc)4·2H2O in a molar ratio of Cu/L = 4 (5.6 wt% gelator concentration), from which 1D coordination polymers [Cu2L(μ-OAc)2(μ-OH)] (1) and coordination nanoclusters {[Cu9L4(OAc)7(OH)5]2+}2 (3) were afforded. The nanoclusters 3 stabilize the 1D coordination polymers 1 and inhibit crystallization of 1 from the system, generating a coordination-based heat-set nanocomposite hydrogel at room and higher temperatures that flows upon cooling to 4 °C, in sharp contrast to most supramolecular gels. Reversible thermo and pH responsive solution–gel phase transitions were observed. The results described herein may open a novel avenue for functional coordination nanocomposite materials.
Co-reporter:Jing Huang, Hongmiao Li, Jianyong Zhang, Long Jiang, Cheng-Yong Su
Inorganica Chimica Acta 2012 Volume 388() pp:16-21
Publication Date(Web):15 June 2012
DOI:10.1016/j.ica.2012.03.004
The N,O ligand, namely 5-(pyridin-4-yl)isophthalic acid (LH2), with carboxylic acid groups and pyridyl group separated, prefers to act as a bridging ligand. Its Tb(III) coordination polymer, [TbL(LH)(H2O)2]∞·xH2O (1), and heterometallic Tb(III)–Ni(II) coordination polymer, [TbNiL2(LH)(H2O)]∞·xH2O (2), have been successfully prepared. Complex 1 exhibits a two-dimensional layered structure with (4,4) network leaving all the pyridyl N-donors uncoordinated, while complex 2 has a three-dimensional structure due to coordination of Ni(II) to part of pyridyl N-donors. Both the complexes were characterized by single-crystal X-ray diffraction, X-ray powder diffraction, FT-IR spectroscopy and thermogravimetry analysis. The ligand is capable of sensitizing the Tb(III) ion, and both the complexes emit characteristic visible green luminescence of Tb(III).Graphical abstractTb(III) and heterometallic Tb(III)–Ni(II) coordination polymers have been synthesized by using 5-(pyridin-4-yl)isophthalic acid as N,O ligand. Their structures were determined by single-crystal X-ray diffraction and their luminescent properties were analyzed.Highlights► Syntheses of Tb(III) and Tb(III)–Ni(II) coordination polymers based on pyridyl dicarboxylate. ► The lanthanide and transition metal ions have different affinities for the N- and O-donors. ► Dimensional increase is observed from 2D to 3D after Ni(II) is introduced. ► The coordination polymers emit green luminescence of Tb(III).
Co-reporter:Jing Huang;Xiaobing Wang
Journal of Inorganic and Organometallic Polymers and Materials 2012 Volume 22( Issue 4) pp:686-691
Publication Date(Web):2012 July
DOI:10.1007/s10904-011-9596-1
A novel microporous one-dimensional heterometallic coordination polymer has been assembled based on a hybrid phosphine ligand, 3,5-bis(diphenylphosphino)benzoic acid, Ag5Cl4 saddle units, and Mn2+. The complex was characterized by a variety of techniques, including single-crystal X-ray diffraction, X-ray powder diffraction, IR, TGA, and microanalysis. Single crystal X-ray analysis shows that the phosphine–Ag5Cl4 saddle units are connected by Mn(II) ions to form 1D beaded coordination chains; and, the 1D coordination chains are parallel-packed via π–π interactions to result in permanent microporosity. The complex represents a rare example of porous 1D coordination polymers as evidenced in a nitrogen adsorption investigation (Langmuir surface area, 307 m2 g−1).
Co-reporter:Sujuan Wang, Lei Li, Jianyong Zhang, Xiaochen Yuan and Cheng-Yong Su
Journal of Materials Chemistry A 2011 vol. 21(Issue 20) pp:7098-7104
Publication Date(Web):31 Mar 2011
DOI:10.1039/C1JM10394F
A structurally flexible porous metal–organic framework, [CuII(bped)2(H2O)2(SiF6)] ⊃ 4H2O (Cu-MOF-SiF6) was prepared from CuSiF6 and meso-1,2-bis(4-pyridyl)-1,2-ethanediol (bped) in EtOH–H2O. Cu-MOF-SiF6 is a three-dimensional (3D) polycatenated framework consisting of two-dimensional (2D) (4,4) topological grid networks which display 2-fold inclined interpenetration in the crystal lattice. The SiF62− anions hosted in the one-dimensional channels of Cu-MOF-SiF6 can be readily exchanged with NO3− anions while keeping the framework intact, leading to isomorphous Cu-MOF-NO3. The Cu-MOFs show selective adsorption behaviors due to the host–guest interaction, which is dependent on the anions and the guest size. The MeOH uptake investigation indicates that Cu-MOF-SiF6 demonstrates a breathing effect, while Cu-MOF-NO3 exhibits distinctive stepwise MeOH sorption due to the smaller size of NO3− and the larger voids in the crystal lattice. Cu-MOF-NO3 also exhibits stepwise sorption for larger EtOH guests, while the uptake of EtOH is blocked in Cu-MOF-SiF6. In addition, the solids show anion-responsive catalytic properties. Both Cu-MOF-SiF6 and Cu-MOF-NO3 efficiently oxidize benzylic compounds to the corresponding carbonyl functionality under mild and convenient reaction conditions, but improved catalytic activity was observed for Cu-MOF-NO3. The catalysts can be reused with the framework left intact at least three times without losing of any activity.
Co-reporter:Xiaobing Wang, Jing Huang, Shenglin Xiang, Yu Liu, Jianyong Zhang, Andreas Eichhöfer, Dieter Fenske, Shi Bai and Cheng-Yong Su
Chemical Communications 2011 vol. 47(Issue 13) pp:3849-3851
Publication Date(Web):14 Feb 2011
DOI:10.1039/C0CC05235C
Ag6L6-type coordination nanotubular structures have been assembled from 6 Ag(I) ions and 6 T-shaped ligands, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine; the nanotubes represent a discrete molecular architecture of a number of polymeric structures assembled from dimeric building blocks.
Co-reporter:Shenglin Xiang ; Jing Huang ; Lei Li ; Jianyong Zhang ; Long Jiang ; Xiaojun Kuang ;Cheng-Yong Su
Inorganic Chemistry 2011 Volume 50(Issue 5) pp:1743-1748
Publication Date(Web):January 19, 2011
DOI:10.1021/ic102188v
Two nanotubular metal−organic frameworks (MOFs), {Cu(L1)·2H2O·1.5DMF}∞ (1) and {Cu2(L2)2(H2O)2·7H2O·3DMF}∞ (2), with novel topologies have been constructed based on Cu2+, 5-(pyridin-4-yl)isophthalic acid (L1) and 5-(pyridin-3-yl)isophthalic acid (L2), respectively. Two MOFs were characterized by IR spectroscopy, thermogravimetry, single-crystal, and powder X-ray diffraction methods. Network analysis reveals a two-nodal (3,6)-connected (4·62)2(42·610·83) net and a three-nodal (3,4)-connected (4·82)4(42·82·102)2(84·122) net. Interpenetration is inherently prevented by both of the topologies of the frameworks. The porosity of MOF 1 was confirmed by N2 and CO2 gas adsorption investigations. MOF 1 exhibits remarkable hydrogen sorption hysteresis at low pressure and a H2 uptake capacity of 1.05 wt % at 77 K and 1 atm.
Co-reporter:Dr. Jianyong Zhang;Shubin Chen;Shenglin Xiang;Jing Huang; Liuping Chen ; Cheng-Yong Su
Chemistry - A European Journal 2011 Volume 17( Issue 8) pp:2369-2372
Publication Date(Web):
DOI:10.1002/chem.201003070
Co-reporter:Yetong Liao, Lisi He, Jing Huang, Jianyong Zhang, Lin Zhuang, Hui Shen and Cheng-Yong Su
ACS Applied Materials & Interfaces 2010 Volume 2(Issue 8) pp:2333
Publication Date(Web):July 15, 2010
DOI:10.1021/am100354b
Functional nanoscale coordination polymers are receiving growing scientific interest because of their potential applications in many domains. In this paper, we demonstrated that a nanofibrous networked metal−organic gel (G1-MNPs) was formed by simply mixing 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tris(N-(pyridin-3-ylmethyl)benzamide) (L) and Pd(COD)(NO3)2 in CHCl3-MeOH with a Pd/L molar ratio of 1:1 in the presence of magnetite nanoparticle (MNPs). The self-assembly behavior of nanofibers was not significantly effected by the introduction of magnetite nanoparticles. The xerogel of G1-MNPs was superparamagnetic and showed catalytic activity in Suzuki-Miyaura C−C coupling reactions. The Pd(II) xerogel could be magnetically isolated and recycled with a permanent magnet. It represents a novel strategy to introduce nanoparticles into functional coordination polymers for multifunctional materials.Keywords: C−C coupling; metal−organic gel; multifunctional material; Pd
Co-reporter:Xiaobing Wang, Jingzhi Feng, Jing Huang, Jianyong Zhang, Mei Pan and Cheng-Yong Su
CrystEngComm 2010 vol. 12(Issue 3) pp:725-729
Publication Date(Web):08 Oct 2009
DOI:10.1039/B916921K
A rare 2D (4,82) Ag-phosphine coordination polymer, [AgL(CF3SO3)]n⊃nDMF has been assembled from Ag+ and a pyridyl diphosphine, 3-(3,5-bis(diphenylphosphino)phenyl)pyridine (L). There exist 16-membered Ag2L2 and 28–membered Ag4L4 macrocyclic rings in the network. However, interestingly, no discrete space is located inside the grids of the layer and its amphiphilic cavities result from interdigitating of the 2D layers. The cavity ridges and hollows are constructed by the PPh2 phenyl rings, and the triflate anions and pyridyl rings, respectively. The layered coordination polymer showed the ability to reversibly selectively uptake guest molecules (DMF) via synergetic weak C–H⋯F/O interactions in its amphiphilic cavities. The results suggest that tuning of cavity microenvironment is important in the design of dynamic guest-responsive materials.
Co-reporter:Jing Huang, Lisi He, Jianyong Zhang, Liuping Chen, Cheng-Yong Su
Journal of Molecular Catalysis A: Chemical 2010 317(1–2) pp: 97-103
Publication Date(Web):
DOI:10.1016/j.molcata.2009.11.001
Co-reporter:Qing Wang, Jianyong Zhang, Chun-Feng Zhuang, Yu Tang and Cheng-Yong Su
Inorganic Chemistry 2009 Volume 48(Issue 1) pp:287-295
Publication Date(Web):November 26, 2008
DOI:10.1021/ic801770n
Cd(II)/Mn(II) coordination grid networks containing large meshes have been assembled from a long rigid ligand, 2,5-bis(4′-(imidazol-1-yl)benzyl)-3,4-diaza-2,4-hexadiene (ImBNN), and M(CF3SO3)2 (M = Cd and Mn) salts, and their interpenetration change upon guest inclusion has been investigated with a series of aromatic molecules. Without guest molecules, the grid networks are triply interpenetrated to form closely packed layer structures [M(ImBNN)2(CF3SO3)2]n (M = Cd (1) and Mn (2)), but when guest molecules are introduced, the triply interpenetrated frameworks are changed to doubly interpenetrated ones with the inclusion of various aromatic molecules, namely, {[M(ImBNN)2(CF3SO3)2]⊃guest}n (M = Cd, guest = o-xylene (3), naphthalene (4), phenanthrene (5), and pyrene (6); M = Mn, guest = benzene (7), p-xylene (8), naphthalene (9), phenanthrene (10), and pyrene (11)). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, and IR spectra. The guest-inclusion/desorption behaviors of representative complexes have been studied by thermogravimetric analyses and 1H NMR measurements. The grid networks display strong preference for aromatic guest inclusion, but less selectivity toward shape and size difference. Tuning of network interpenetration from 3-fold to 2-fold has been successfully achieved through the introduction of guest molecules, when the network displays flexibility to change cavity size to match the guest molecules.
Co-reporter:Jianyong Zhang, Xiaobing Wang, Lisi He, Liuping Chen, Cheng-Yong Su and Stuart L. James
New Journal of Chemistry 2009 vol. 33(Issue 5) pp:1070-1075
Publication Date(Web):24 Feb 2009
DOI:10.1039/B822104A
Modification of Fe-tricarboxylate based metal–organic gels yielded tert-butyl substituted or phosphine-functionalised gels in alcohols or DMF, which were prepared from 5-tert-butylisophthalic acid and 5-diphenylphosphanylisophthalic acid, respectively. Owing to their permeability, such phosphine-functionalised metal–organic gels can act as a new type of functionalisable porous scaffold. The phosphorus-containing gel was subsequently functionalised with Pd(II) by immersion in a solution of Pd(COD)Cl2 (COD = 1,5-cyclooctadiene). The subsequently functionalised Pd(II)-immobilised gel and its xerogel/aerogel showed high activity in the catalysis of Suzuki C–C coupling comparable to unsupported complexes. The gel/xerogels could be reused under ambient atmosphere.
Co-reporter:Jian-Yong Zhang, Li-Hua Zeng, Juan Feng
Chinese Chemical Letters (February 2017) Volume 28(Issue 2) pp:
Publication Date(Web):February 2017
DOI:10.1016/j.cclet.2016.07.015
Dynamic covalent chemistry has emerged recently to be a powerful tool to construct functional materials. This article reviews the progress in the research and development of dynamic covalent chemistry in gels assembled from small molecules. First dynamic covalent reactions used in gels are reviewed to understand the dynamic covalent bonding. Afterwards the catalogues of dynamic covalent gels are reviewed according to the nature of gelators and the interactions between gelators. Dynamic covalent bonding can be involved to form low molecular weight gelators. Low molecular weight molecules with multiple functional groups react to form dynamic covalent cross-linked polymers and act as gelators. Two catalogues of gels show different properties arising from their different structures. This review aims to illustrate the structure–property relationships of these dynamic covalent gels.This article reviews the progress in the research and development of dynamic covalent chemistry in low molecular weight gels and dynamic covalent polymer gels assembled from small molecules.
Co-reporter:Xin Tan, Xue Chen, Jianyong Zhang and Cheng-Yong Su
Dalton Transactions 2012 - vol. 41(Issue 13) pp:NaN3619-3619
Publication Date(Web):2012/02/09
DOI:10.1039/C2DT00035K
Rigid bridging terpyridyl phosphine and AgOTf form nanofibres to induce gelation of organic solvents, and the gel emits blue luminescence by suppressing π–π interactions between ligands.
Co-reporter:Sujuan Wang, Lei Li, Jianyong Zhang, Xiaochen Yuan and Cheng-Yong Su
Journal of Materials Chemistry A 2011 - vol. 21(Issue 20) pp:NaN7104-7104
Publication Date(Web):2011/03/31
DOI:10.1039/C1JM10394F
A structurally flexible porous metal–organic framework, [CuII(bped)2(H2O)2(SiF6)] ⊃ 4H2O (Cu-MOF-SiF6) was prepared from CuSiF6 and meso-1,2-bis(4-pyridyl)-1,2-ethanediol (bped) in EtOH–H2O. Cu-MOF-SiF6 is a three-dimensional (3D) polycatenated framework consisting of two-dimensional (2D) (4,4) topological grid networks which display 2-fold inclined interpenetration in the crystal lattice. The SiF62− anions hosted in the one-dimensional channels of Cu-MOF-SiF6 can be readily exchanged with NO3− anions while keeping the framework intact, leading to isomorphous Cu-MOF-NO3. The Cu-MOFs show selective adsorption behaviors due to the host–guest interaction, which is dependent on the anions and the guest size. The MeOH uptake investigation indicates that Cu-MOF-SiF6 demonstrates a breathing effect, while Cu-MOF-NO3 exhibits distinctive stepwise MeOH sorption due to the smaller size of NO3− and the larger voids in the crystal lattice. Cu-MOF-NO3 also exhibits stepwise sorption for larger EtOH guests, while the uptake of EtOH is blocked in Cu-MOF-SiF6. In addition, the solids show anion-responsive catalytic properties. Both Cu-MOF-SiF6 and Cu-MOF-NO3 efficiently oxidize benzylic compounds to the corresponding carbonyl functionality under mild and convenient reaction conditions, but improved catalytic activity was observed for Cu-MOF-NO3. The catalysts can be reused with the framework left intact at least three times without losing of any activity.
Co-reporter:Lihua Zeng, Peisen Liao, Haoliang Liu, Liping Liu, Ziwei Liang, Jianyong Zhang, Liuping Chen and Cheng-Yong Su
Journal of Materials Chemistry A 2016 - vol. 4(Issue 21) pp:NaN8336-8336
Publication Date(Web):2016/04/26
DOI:10.1039/C6TA01035K
A series of (metallo)porphyrin imine gels have been synthesized based on imine chemistry. The resulting aerogels have sponge-like porous networked structures consisting of interconnected nanoparticles with hierarchical porosity. The aerogels have high specific surface areas (up to 719 m2 g−1) and large pore volumes (up to 2.60 cm3 g−1). The effect of metal ions on the uptake of gases in these aerogels was investigated. The impregnation of various metal ions (Pd(II), Ni(II), Mn(III), Fe(III) and Sn(IV)) enhances the uptake capacity of various gases (e.g., CO2) despite their higher densities. Among the metal ions, Pd(II) is the best to increase the adsorption capacity and the isosteric heat of CO2 adsorption. The Pd-tapp–A4 aerogel exhibits CO2 volumetric uptake (1.62 mmol g−1, 7.13 wt% at 298 K, 1 bar) with a high isosteric heat of adsorption (40.0 kJ mol−1). The gels also show potential applications in catalysis because of their unique hierarchical porosity and the availability of metal centers. In combination with microfluidic technology, a catalytic gel capillary reactor has been assembled with the Pd-tapp–A4 gel supported on the inner surface of a functionalized capillary.
Co-reporter:Jianyong Zhang, Liping Liu, Haoliang Liu, Minjuan Lin, Siyan Li, Gangfeng Ouyang, Liuping Chen and Cheng-Yong Su
Journal of Materials Chemistry A 2015 - vol. 3(Issue 20) pp:NaN10998-10998
Publication Date(Web):2015/04/14
DOI:10.1039/C5TA00557D
A series of novel aerogels have been obtained based on imine chemistry. The aerogels were prepared by polycondensation of various bridging aldehydes and amines via a sol–gel process. The imine aerogels of tetrakis-(4-aminophenyl)methane (A1) consist of three-dimensional networks of interconnected nanometer-sized particles with hierarchically porous structures. The porosity of the areogels is tuneable by the choice of precursors, precursor concentration and reaction solvent. The aerogels exhibit BET surface areas up to 1021 m2 g−1 (A1-biformyl aerogel A1B1-0.030), as measured by N2 adsorption at 77 K. The A1B1-0.030 aerogel possesses a CO2 uptake of 1.5 mmol g−1 at 298 K and 1.0 bar with an isosteric heat of 38.1 kJ mol−1 and displays high CO2/N2 selectivity up to 70.9, which is derived from the ideal adsorbed solution theory. The A1B1-0.030 aerogel also shows a good capacity to uptake aromatic toluene molecules from an aqueous solution. Moreover, the hierarchically porous structure endows the A1B1-0.030 aerogel with good performance in enrichment of large molecules (polycyclic aromatic hydrocarbons PAHs and organochlorine pesticides OCPs) as the coating adsorbent in solid-phase microextraction (SPME) fibres.
Co-reporter:Xiaobing Wang, Jing Huang, Shenglin Xiang, Yu Liu, Jianyong Zhang, Andreas Eichhöfer, Dieter Fenske, Shi Bai and Cheng-Yong Su
Chemical Communications 2011 - vol. 47(Issue 13) pp:NaN3851-3851
Publication Date(Web):2011/02/14
DOI:10.1039/C0CC05235C
Ag6L6-type coordination nanotubular structures have been assembled from 6 Ag(I) ions and 6 T-shaped ligands, 4-(3,5-bis(diphenylphosphino)phenyl)pyridine; the nanotubes represent a discrete molecular architecture of a number of polymeric structures assembled from dimeric building blocks.
Co-reporter:Jianyong Zhang, Qiuli Yang, Yixuan Zhu, Haoliang Liu, Zhenguo Chi and Cheng-Yong Su
Dalton Transactions 2014 - vol. 43(Issue 42) pp:NaN15790-15790
Publication Date(Web):2014/08/18
DOI:10.1039/C4DT01808G
A tetraphenylethylene-based phosphine, 1,1,2,2-tetrakis((4-diphenylphosphino)phenyl)ethylene (TPE-P4), was synthesized and showed novel aggregation-induced and mechano-responsive emission. A mixture of TPE-P4 and Ag+ could fix atmospheric CO2in situ as carbonate ions in neutral solution to yield a rare 3D metal–organic framework with zeolite-like SOD topology, [Ag2(TPE-P4)CO3]x⊃nH2O (Ag-TPE-P4). Ag-TPE-P4 showed turn-on luminescence of TPE-P4, emitting bright bluish green light in the solid state.
Co-reporter:Weijun Luo, Yixuan Zhu, Jianyong Zhang, Jiajun He, Zhenguo Chi, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Communications 2014 - vol. 50(Issue 80) pp:NaN11945-11945
Publication Date(Web):2014/08/14
DOI:10.1039/C4CC05120C
A novel dynamic covalent gel has been prepared via the imine bond formation reaction of tetraamine building blocks with luminescent tetraphenylethene tetraaldehyde units. The gel shows high hierarchical porosity (SBET = 512 m2 g−1) and remarkable aggregation-induced emission enhancement, which has been demonstrated to be a selective sensor.
Co-reporter:Haoliang Liu, Juan Feng, Jianyong Zhang, Philip W. Miller, Liuping Chen and Cheng-Yong Su
Chemical Science (2010-Present) 2015 - vol. 6(Issue 4) pp:NaN2296-2296
Publication Date(Web):2015/02/18
DOI:10.1039/C5SC00314H
A novel dynamic covalent gel strategy is reported to immobilize an asymmetric catalyst within the channels of a microfluidic flow reactor. A layer of a catalytically active Mn–salen dynamic covalent imine gel matrix was coated onto a functionalized capillary. Mn–salen active moiety was incorporated into dynamic covalent imine gel matrix via the reaction of a chiral Mn–salen dialdehyde unit with a tetraamine linker. The catalytic activity of the capillary reactor has been demonstrated in enantioselective kinetic resolution of secondary alcohols.
Co-reporter:Juan Feng, Liu Yao, Jianyong Zhang, Yingxiao Mu, Zhenguo Chi and Cheng-Yong Su
Dalton Transactions 2016 - vol. 45(Issue 4) pp:NaN1673-1673
Publication Date(Web):2015/12/14
DOI:10.1039/C5DT04319K
A novel phosphine-based tetragonal Ag4L2 cage has been assembled from a tetraphenylethylene (TPE)-based tetraphosphine and Ag+ ions. The cage structure is maintained both in solutions and in the solid state. Ag4L2 emits strong fluorescence not only in dilute solutions but also in aggregated states. The turn-on fluorescence of TPE-P4 in dilute solutions is attributed to the formation of Ag4L2. Ag4L2 shows potential as a fluorescent sensor towards anions and olefin compounds, which arises from binding of the guest anions/olefin compounds by its labile silver centres.
Co-reporter:Shenglin Xiang, Lei Li, Jianyong Zhang, Xin Tan, Huanan Cui, Jianying Shi, Yuling Hu, Liuping Chen, Cheng-Yong Su and Stuart L. James
Journal of Materials Chemistry A 2012 - vol. 22(Issue 5) pp:
Publication Date(Web):
DOI:10.1039/C1JM14618A
Co-reporter:Juan Feng, Hongmiao Li, Qiuli Yang, Shi-Chao Wei, Jianyong Zhang and Cheng-Yong Su
Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 4) pp:NaN394-394
Publication Date(Web):2015/02/04
DOI:10.1039/C4QI00138A
Two porous coordination polymers, Co-Py2PO and Co-Py2PO′, have been obtained via reactions of in situ oxidized terpyridyl phosphines and cobalt(II) nitrate. Single-crystal structure analysis reveals that Co-Py2PO′ has a three-dimensional (3D) structure with (8·102)(83) net topology, while the structural analysis of Co-Py2PO reveals a 2D polycatenated framework consisting of two sets of parallel 2D networks of (63) net topology. For Co-Py2PO′, guest CHCl3 molecules are locked in the channels along the b axis by P(O)Ph2 phenyl rings and coordinated nitrate ions, and cannot be released out of the host framework. In contrast, the as-synthesized 2D framework Co-Py2PO readily loses its solvated guest molecules to give an activated amorphous material for sorption. Activated Co-Py2PO has a flexible structure and shows dynamic adsorption behaviours towards various guests (N2 and benzene). The flexibility may arise from the combination of layer–layer motion and the local flexibility of the P–C bond of –P(O)Ph2 groups.
![Ethanone,1-[1,1'-biphenyl]-2-yl-](http://img.cochemist.com/ccimg/2200/2142-66-7.png)
![Ethanone,1-[1,1'-biphenyl]-2-yl-](http://img.cochemist.com/ccimg/2200/2142-66-7_b.png)
