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[Zn(3-tba)2], 1, a 1-D coordination polymer synthesised as 1 DMA, 1α, transformed to a nonporous form, 1β, upon activation. 1β underwent further transformation to the dimeric complex [Zn(3-tba)2(H2O)2], 2, above 40% RH. The reverse transformations, 2 to 1β and 1β to 1α, were accomplished by heating and exposure to DMA, respectively, and were single-crystal-to-single-crystal phase changes. Single crystal X-ray diffraction revealed that the second transformation resulted from Zn–carboxylate bond breakage and concomitant coordination of water molecules. Other solvent molecules did not induce a phase change

In the title compound, [NiCl

A three-dimensional (3D) metal–organic framework [(CH3)2NH2][Zn2(DMTDC)2(3-mtz)]·4DMF·3H2O (Zn-MOF) has been solvothermally synthesized by using mixed ligands of 3-methyl-1,2,4-triazole (3-Hmtz) and a thiophene-functionalized dicarboxylate ligand, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DMTDC). Zn-MOF exhibits a uninodal 6-connected pcu α-Po topology structure and possesses an anionic framework with large 1D-trapezoidal channels. Gas adsorption studies reveal that the activated Zn-MOF-a displays selective adsorption of CO2 over N2 at 273 K and 298 K as well as a high isosteric heat of CO2 adsorption. Moreover, Zn-MOF shows selective adsorption of the cationic dyes over the anionic and neutral dyes, and can be used as a fast-response and sensitive probe for the detection of Fe3+ by fluorescence quenching after encapsulation of Tb3+ into the pores by postsynthetic cation exchange.

Three new alkaline earth metal–organic frameworks (MOFs), namely [Mg2(DMTDC)2(DMF)3(H2O)2]·2DMF·2H2O (1), [Ca(DMTDC)(DMF)] (2) and [Sr(DMTDC)(DMF)] (3), have been synthesized under solvothermal conditions by using a thiophene-functionalized dicarboxylate ligand, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DMTDC). Single-crystal X-ray diffraction analyses demonstrate that the metal ion radii play an important role in coordination numbers and topologies, i.e., hexa-coordinated Mg2+ in 1 gives a two-dimensional layered framework with an sql net, while octa-coordinated Ca2+/Sr2+ in 2/3 exhibit a three-dimensional framework with lvt nets. All frameworks show a one-dimensional rhombus-shaped channel that is occupied by DMF and/or water molecules. Photoluminescence studies reveal that 1–3 can be used as fast-response fluorescence sensors for the sensitive detection of Fe3+ ions with favorable recyclability through fluorescence quenching.

Photoluminescent alginate hydrogels containing covalently linked YVO4–Eu3+ have been prepared by using a facile method. The environmentally friendly preparation procedure was carried out at room temperature using water as a solvent. The photoluminescent hydrogels showed outstanding acetone sensing properties with quick response, high sensitivity, short recovery time and good reversibility.

peer-reviewed We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn2(DMTDC)2(dpe)] (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene), that exhibits reversible switching between an as-synthesized “open” phase, X-pcu-5-Zn-α, and two nonporous or “closed” polymorphs, X-pcu-5-Zn-β and X-pcu-5-Zn-γ. There are two unusual features of X-pcu-5-Zn. The first relates to its sorption properties, which reveal that the α form exhibits high CO2 uptake (ca. 255 cm3/g at 195 K) via reversible closed-to-open switching (type F-IV isotherm) of the type desirable for gas and vapor storage; there are only three other reports of porous materials that combine these two features. Second, we could only isolate the β form by activation of the CO2 loaded α form and it persists through multiple CO2 adsorption/desorption cycles. We are unaware of a new polymorph having been isolated in such a manner. That the observed phase changes of X-pcu-5-Zn-α occur in single-crystal-to-single-crystal fashion enabled structural characterization of the three forms; γ is a coordination isomer of α and β, both of which are based upon “paddlewheel” clusters. The full text of this article will not be available in ULIR until the embargo expires on the 05/11/2019

A new 3D zinc coordination polymer, namely {[Zn4(dmtz)3(OH)3(HCOO)](NO3)}n (1, Hdmtz = 3,5- dimethyl-1,2,4-triazole), is hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction analysis. The complex features a (3,4,5)- connected 3D cation framework constructed by μ3-bridging dmtz with hydroxyl and formate anions as the auxiliary ligands. Moreover, the photocatalytic properties of 1 are also investigated.

A novel metal-organic framework formulated as [Mn(DMTDC)(DMF)] (1) was synthesized under solvothermal conditions by using a thiophene-functionalized dicarboxylate ligand, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DMTDC), which displays a uninodal, 4-connected lvt net. After the removal of coordinated DMF, this framework displays permanent porosity and excellent photocatalytic activity for methylene blue (MB) dye degradation in aqueous solution under UV light.

Two lanthanide–organic frameworks formulated as [Eu2(DMTDC)3(DEF)4]·DEF·6H2O (1) and [Tb2(DMTDC)3(DEF)4]·DEF·6H2O (2) (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid and DEF = N,N-diethylformamide) have been synthesized under solvothermal conditions by using a bithiophene dicarboxylate organic ligand, H2DMTDC. Compounds 1 and 2 are isomorphous and feature 3D frameworks with uninodal six-connected pcu α-Po topology structures. The systematic luminescence experiments reveal that 1 and 2 can be used as fast-response fluorescence sensors for the sensitive detection of nitrobenzene and Fe3+ ions with favorable recyclability through fluorescence quenching.

The coordination compounds, [Cu2(Htba)(tba)Cl] (1) and [Ag2(Htba)(tba)(NO3)] (2), were synthesized under solvothermal conditions by using a triazolate-carboxylate bifunctional organic ligand 4-(4H-1,2,4-triazol-4-yl)benzoic acid (Htba). X-ray single crystal diffraction analyses for the two complexes revealed that compounds 1 and 2 exhibit one-dimensional (1D) chain structures with uncoordinated carboxylic groups, which are further connected by O–H···O hydrogen bonds into 3D, threefold interpenetrating supramolecular frameworks with different topologies belonging to 4-connected and (2,4)-connected nets with the (42·82·102)(43·62·8)2(44·62) and (125·16)(12)2 Schlafli symbols, respectively. The photoluminescent measurements reveal that both 1 and 2 exhibit bluish-purple emissions in the solid state at room temperature. In addition, the compound 2 can serve as an antenna for sensitizing the visible-emitting of the lanthanide cations to display their characteristic emissions.

peer-reviewed Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu‐topology MOF, X‐pcu‐5‐Zn, have been prepared: X‐pcu‐6‐Zn, 6=1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn, 7=1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn, 8=4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N2, CO2, C2H2, and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.

Biocompatible luminescent hydrogels containing covalently linked terbium complexes with a macrocyclic ligand are prepared by a facile method. The environmentally friendly preparation procedure is carried out at room temperature using water as a solvent. These new hybrid materials can act as luminescent sensors to detect Fe3+ with relative selectivity and high sensitivity. The hydrogels also show pH sensing with a wide range.

A luminescent zinc metal-organic framework with uncoordinated triazolate N-donors, namely [Zn (tba)2]·DMA (1, DMA ​= ​N,N-dimethylacetamide), has been successfully synthesized under solvothermal conditions by using a triazolate-carboxylate bifunctional ligand, 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Htba). Single-crystal X-ray diffraction analysis reveals that compound 1 displays a 4-fold interpenetrating dia framework with 1D dumbbell-shaped channels. The systematic luminescence experiments reveal that 1 can be potentially used as a fast-response fluorescence sensor for the sensitive detection of nitrobenzene and Fe3+ ion through drastic fluorescence quenching. Moreover, the quenching mechanisms of 1 towards nitrobenzene and Fe3+ were also investigated.

The copper-iodine based coordination polymer [Cu4I2(bmte)]n (1) [H2bmte = 1,2-bis(5-methyl-1H-1,2,4-triazol-3-yl)ethane] was synthesized using cuprous iodide and a flexible 3-substituted, ethyl-bridging bis(triazole) ligand under solvothermal conditions. X-ray diffraction analysis reveals that compound 1 shows a 3D framework containing Cu4I4 clusters and alternating left- and right-handed [Cu(triazole)] helices, which result in a (4,8)-connected fluorite (flu) topological network. Moreover, compound 1 exhibits orange phosphorescence with the emission maxima at 590 nm in the solid state at room temperature.

Five novel Cd(II) complexes, [Cd2(3-tba)4(H2O)4]·4H2O (1), [Cd(3-tba)Cl] (2), [Cd(3-tba)I] (3), [Cd2(3-tba)2(SCN)2(H2O)2]·2H2O (4), and [Cd3(3-tba)2(SO4)2(H2O)2] (5), were synthesized under hydrothermal conditions by the reaction of different Cd(II) salts with a V-shaped, bifunctional triazole-carboxylate ligand 3-(4H-1,2,4-triazole-4-yl)benzoic acid (3-Htba). X-ray single crystal diffraction analyses for these complexes revealed that compounds 1 and 2 exhibit a binuclear motif and a 3D binodal (3,5)-connected fsf/polar network, respectively, whereas 3 and 4 show 2D layer structures with different topologies belonging to 4-connected sql and (3,4)-connected V2O5 net, respectively. Complex 5 exhibits a 3D (3,4,5)-connected network with the (42·6)2(42·83·10)(43·63)2(44·64·82)2 Schlafli symbol. All the complexes were characterized using single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and elemental analyses. In addition, the solid-state photoluminescence results for 1–5 were also investigated.

Seven coordination compounds, namely [Zn(4-tba)2(H2O)2] (1), [Zn(4-tba)Cl]·CH3OH (2), [Zn(4-tba)2] (3), [Zn(4-tba)2]·DMA·3.5H2O (4), [Cd(4-tba)2]·DMF·3.6H2O (5), [Cd(4-tba)2] (6) and [Cd5Cl4(4-tba)6]·1.5DMF·4H2O (7) (4-Htba = 4-(4H-1,2,4-triazol-4-yl)benzoic acid, DMA = N,N-dimethylacetamide and DMF = N,N-dimethylformamide), have been synthesized under hydro/solvothermal conditions by using a triazolate–carboxylate bifunctional organic ligand, 4-Htba. Complexes 1 and 2 exhibit a mononuclear motif and a two-dimensional (2D) network with sql topology, respectively, whereas 3–6 display different interpenetrating structures. Compound 3 shows a 2-fold interpenetrating 2D net with sql topology, 4 and 5 display uninodal 4-connected 4-fold interpenetrating 3D nets with dia (66) topology belonging to class Ia and class IIIa, respectively, and compound 6 exhibits a 5-fold interpenetrating dia net. Complex 7 exhibits a non-interpenetrating 3D framework constructed from decanuclear cadmium–chloride chain units and 4-tba ligands with various coordination modes. All the complexes were characterized using single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and elemental analyses. In addition, the thermogravimetric analysis and solid-state photoluminescence results for 1–7 were also investigated.

The photocatalytic reduction of CO2 to CH4 in a hydrous solution was successfully achieved by a homogeneous molecular catalytic system involving two dinuclear nickel complex catalysts (i.e., [(dmbpy)2Ni2Cl4(H2O)2] (1) (dmbpy = 4,4′-dimethyl-2,2′-bipyridine) and [(bpy)2Ni2Cl4(H2O)2] (2) (bpy = 2,2′-bipyridine)), in the presence of [Ru(bpy)32+] or organic dye such as Eosin Y as a photosensitizer. Control and cyclic voltammetry experiments (CV) revealed that H2O could provide the H+ required for the conversion of CO2 into CH4 and ruled out CO as an intermediate in this reaction.

A luminescent cadmium metal–organic framework functionalized with uncoordinated triazolate N-donors has been constructed by using a triazolate–carboxylate bifunctional organic ligand. It exhibits selective adsorption of CO2 over N2 behavior, and interesting guest-dependent photoluminescence properties.

Via chemical etching, the pillar ligands of a 3D metal-organic frameworks (MOF) were removed, and a 2D layer MOF was obtained. This 2D MOF possesses high density of open metal...

Three isoreticular metal-organic frameworks based on ternary zinc(II)/triazolate/X (X = OAc−, Cl−) metal azolate frameworks, namely [Zn(mtz)(OAc)]·H2O (1, Hmtz = 3-methyl-1,2,4-triazole), [Zn(etz)(OAc)]·0.5H2O (2, Hetz = 3-ethyl-1,2,4-triazole) and [Zn(metz)Cl]·0.25H2O (3, Hmetz = 3-methyl-5-ethyl-1,2,4-triazole), have been synthesized by changing the substituent groups on asymmetric 1,2,4-triazolates and auxiliary anions (OAc− or Cl−). These frameworks have a 3-connected 4.8.10-lvt-a topological network, which can be also simplified into a 4-connected lvt net by further denoting dinuclear [Zn2(triazole)2] subunits as a square-planar 4-connected node. 1 exhibits a porous structure with 1D (d = 3.0 A) effective channels showing the selective adsorption behaviors of CO2 over N2, whereas 2 and 3 are nonporous structures.

Acid–base neutralization reaction between monoalkyl-substituted azole derivatives and ZnO/Zn(OH)2 can be effectively activated by aqueous ammonia to synthesize a series of metal azolate frameworks (MAFs) including SOD-[Zn(mim)2] (MAF-4, Hmim = 2-methylimidazole), ANA-[Zn(eim)2] (MAF-5, Heim = 2-ethylimidazole), SOD-[Zn(mtz)2] (MAF-7, Hmtz = 3-methyl-1,2,4-triazole), dia-[Zn(mim)2] (MAF-31), qtz-[Zn(eim)2] (MAF-32), and dia-[Zn(etz)2] (MAF-33, Hetz = 3-ethyl-1,2,4-triazole). The porous zeolitic MAFs obtained by this reaction possess high stability and can be easily activated. Their high porosity, unique pore size/surface characteristic, and framework flexibility were demonstrated by gas and solvent vapor (water, methanol, and benzene) sorption measurements. The imidazolate frameworks MAF-4 and MAF-5 are highly hydrophobic adsorbents with exceptional organic/water selectivity, while the triazolate framework MAF-7 containing uncoordinated nitrogen donor on the pore surface exhibits higher sorption affinity and lower stability. Despite the very small aperture sizes (3.2–3.4 A), the SOD frameworks can readily adsorb large organic molecules by temporary distortion of the structure.

A series of copper(I)-halide complexes with 4-amino-3,5-dimethyl-1,2,4-triazole (admtz) as bridging ligands, namely, [Cu2Cl2(admtz)2] (1), [Cu2Br2(admtz)2] (2), [Cu4Br4(admtz)4] (3) and [Cu2I2(admtz)2]n (4), have been synthesized under hydrothermal conditions. X-ray single-crystal diffraction reveals that 1 and 2 show discrete dimeric structures, in which hydrogen bonds link the dimers into 2D networks. Complex 3 adopts a discrete tetrameric structure, which is further connected into a 3D network by C–H···Br non-classical hydrogen bonds. Complex 4 displays a 1D chain that is be further extended into a 2D framework by N–H···I weak interactions. The photoluminescent and luminescence lifetime measurements reveal that 1, 2 and 4 exhibit extensive green-blue phosphorescences in the solid state at room temperature, whereas 3 shows much weaker fluorescent emissions and shorter luminescence lifetimes.

A new copper coordination polymer [Cu3(CN)(dmtz)2] (1) (Hdmtz = 3,5-dimethyl-1,2,4-triazole) was solvothermally synthesized and characterized by IR spectroscopy, X-ray power diffraction, and single-crystal X-ray diffraction. The single-crystal diffraction analysis shows that compound 1 belongs to the orthorhombic space group Pmmn, and exhibits a 2D planar framework constructed by the ligand dmtz and cyanide anions, in which the cyanide anion was generated from in situ decomposition of acetonitrile. The photoluminescent study indicates that 1 emits strong blue-green luminescence with long emission lifetimes in the solid state at room temperature.

Natural and synthetic zeolites are important microporous materials. [ 1 ] The highly ordered structures and tunable compositions of aluminosilicate frameworks are responsible for their extraordinary performances. After the discovery of zeolitic metal imidazolate frameworks, ranging from zeolite-like cobalt imidazolates [ 2 ] to the SOD-, ANA-, and RHO-type (three-letter codes of zeolite topologies) zinc benziimidazolate [ 3 ] and 2-alkylimidazolates, [ 4 ] these novel porous coordination polymers (PCPs) have blossomed in the past few years. [ 5 ] The similarity of the bended exo-bidentate coordination mode of imidazolate with that of the O atom in aluminosilicates has been considered as a determinative construction principle ( Figure 1 ). The rich structure-directing role of imidazolate side groups provides an additional variable for enumeration of new zeolitic structures. [ 3–5 ] Nevertheless, there seems to be some inherent difference between the inorganic and metal-organic counterparts. For example, inorganic zeolites are negatively charged aluminosilicate frameworks and their pore surface property can be routinely tailored by adjusting the Al/Si ratio and/or cation exchange. In contrast, PCPs (including metal-organic zeolites) are well-known to be completely ordered materials. Among the large family of known metal-organic zeolites, SOD-[Zn(mim) 2 ] (Hmim = 2-methylimidazole [ 4 ] ) is noteworthy for its high porosity and exceptional stability. The synthesis, porous property, sorption mechanism, and application of MAF-4 (the metal azolate framework 4) have attracted much attention. [ 6 ] However, MAF-4 only adsorbs many important gases, such as H 2 , CO 2 , and C 2 H 2 weakly, due to the lack of a strong adsorption site on its pore surface. While new functionalities of MAF-4 are still emerging, efforts have been devoted to the structural modifi cation of this prototype framework. Because imidazolates are almost the shortest linkers in PCPs, variation of the metal ion and/or substituent groups on the imidazolate linker can largely alter porosity (size or volume), change the framework, [ 5e–h ] and even alter the whole network topology. Metal ion substitution can effectively change the pore surface properties of PCPs functionalized with coordinatively unsaturated metal centers. [ 7 ] However, the tetrahedral

Self-assembly of silver(I) ion with 3-alkyl-1,2,4-triazoles in different solvents yielded four new metal azolate frameworks (MAFs), namely, [Ag(mtz)] (1, Hmtz = 3-methyl-1,2,4-triazole), [Ag(etz)] (2, Hetz = 3-ethyl-1,2,4-triazole), [Ag4(etz)4]·H2O (3·H2O), and [Ag4(ptz)4] (4, Hptz = 3-propyl-1,2,4-triazole). Single-crystal X-ray diffraction revealed that Ag(I) ions and triazolates in these MAFs are all three-coordinated to give rare 3-connected framework topologies. Although 1 and 2 possess the same uniform (10,3)-d (utp) topology, variation of the alkyl groups renders substantially different coordination structures. On the other hand, 3·H2O and 4, also bearing different alkyl substituents, are isomorphours, and can be simplified as the same uninodal sqc5603 topology (point and vertex symbols are 82.10 and 8.82.12, respectively). Due to the relatively short alkyl length, the coordination framework of 3·H2O contains one-dimensional narrow channels. According to thermogravimetry and single-crystal X-ray di...

Binding of four bipyridyl ligands, 2,2′-bipyridine (L1), 1,10-phenanthroline (L2), 1,4,8,9-tetraazatriphenylene (L3), and dipyrido[3,2-a:2′,3′-c]phenazine (L4) with Cdq2/Znq2 complexes (q = 8-hydroxyquinoline) gave four neutral, mononuclear CdII/ZnII complexes, namely [Cdq2L1]·H2O·CH3OH (1), [Cdq2L3]·3H2O (2), [Cdq2L4]·2H2O (3), and [Znq2L4]·2CH3OH (4). These mixed-ligand compounds were taken as models for investigating the interfacial effect at the electron-transfer layer/light-emitting layer junction in OLEDs by combination of X-ray diffraction, fluorophotometric titration, cyclic voltammetry, and time-dependent density functional theory (TDDFT) calculations. The results shows the formation of these compounds is favorable to energy transition on the contact surface. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Control over the structure and property of synthetic materials is crucial for practical applications. Here we report a facile, green and controllable solid-gas reaction strategy for on-demand modification of porous coordination polymer. Copper(I) and a methylene-bridged bis-triazolate ligand are combined to construct a porous crystal consisting of both enzyme-like O2-activation site and oxidizable organic substrate. Thermogravimetry, single-crystal X-ray diffraction, electron paramagnetic resonance and infrared spectroscopy showed that the methylene groups can be oxidized by O2/air even at room temperature via formation of the highly active Cu(II)-O2(˙-) intermediate, to form carbonyl groups with enhance rigidity and polarity, without destroying the copper(I) triazolate framework. Since the oxidation degree or reaction progress can be easily monitored by the change of sample weight, gas sorption property of the crystal can be continuously and drastically (up to 4 orders of magnitude) tuned to give very high and even invertible selectivity for CO2, CH4 and C2H6.

Retraction of ‘Chemical etching of a cobalt-based metal–organic framework for enhancing the electrocatalytic oxygen evolution reaction’ by Ai-Xin Zhu et al., J. Mater. Chem. A, 2017, DOI: 10.1039/c7ta02103h.

In the title solvate, C22H18O6·2C3H7NO, the complete dicarboxylic acid molecule is generated by a crystallographic twofold axis, which bisects the central benzene ring and oneN,N-dimethylformamide solvent molecule. The dihedral angle between the central and pendant benzene rings is 54.53 (5)° while that between the pendant rings is 45.44 (5)°. In the crystal, the acid molecules are linked to the solvent moleculesviaO—H...O and weak C—H...O hydrogen bonds. Further weak C—H...O interactions link adjacent acid molecules into a three-dimensional network.

The two-step N(2) adsorption behaviour of sodalite-type Zn(II) 2-methylimidazolate and 3-methyl-1,2,4-triazolate has been comprehensively and accurately elucidated.

Using a bis-triazolate ligand and tetrahedral Zn(II) ion, we synthesized a flexible porous coordination polymer functionalized with pairs of uncoordinated triazolate N-donors that can be used as guest chelating sites to give very high CO(2) adsorption enthalpy and CO(2)/N(2) selectivity. The dynamic CO(2) sorption behavior could be monitored well by single-crystal X-ray diffraction.

Two pairs of supramolecular isomers based on ternary zinc(II)/triazolate/X (triazolate = 3,5-dimethyl-1,2,4-triazolate (Hdmtz), X = HCOO(-), F(-)) metal azolate frameworks, namely, [Zn(dmtz)(HCOO)] x H(2)O (MAF-X3, 1a), [Zn(dmtz)(HCOO)] x (1/6Me(2)NH)(1/4H(2)O) (MAF-X4, 1b), [Zn(dmtz)F] (MAF-X5, 2a), and [Zn(dmtz)F] (MAF-X6, 2b), have been synthesized via variations of the reaction conditions. The 3-connected Zn(dmtz) networks in 1a, 1b, 2a, and 2b can be described as rarely observed 4.8(2), 4.12(2), (8,3)-b, and 8(2).10-a, respectively. Besides the mu(3)-dmtz, tetrahedral and trigonal-bipyramidal/square-pyramidal coordination of the Zn ions are accomplished by monodentate formate and mu-F, respectively. While 1a and 2b are nonporous structures, 1b and 2a exhibits 1D nanotubular hydrophilic (d 3.2 A) and hydrophobic (d 3.6 A) channels, respectively. Thermogravimetric analysis shows that the stabilities of 2a and 2b are much better than those of 1a and 1b, which may be ascribed to different coordination numbers of zinc atoms. Moreover, 1b and 2a with different pore properties show selective sorption behavior.

Some racemates including alcohol, ketone, flavone, phenol, base, and amide racemates etc. were successfully separated by using a 3D chiral nanoporous metal-organic framework (MOF) as a new chiral stationary phase in HPLC. The experimental results show that the chiral MOF possesses excellent recognition ability for various racemates, and indicate that enantioseparation on the chiral MOF column is practicable.

A 1-D chain-like hybrid coordination polymer [(CuBr)2(bpy)]n (bpy = 2,2′-bipyridine) was first synthesized via a hydrothermal reaction of copper(I) bromide with 2,2′-bipyridine (bpy). The most fascinating feature of [(CuBr)2(bpy)]n is the unusual six-member-(Cu3Br3)-ring motif. The skeleton of copper bromide combined with bpy in [(CuBr)2(bpy)]n has not been reported. In addition, research on pyrolysis of [(CuBr)2(bpy)]n was reported in this paper. Oriented growth of single crystalline Cu(111) flake, which is usually prepared through depositing onto the surface of high-quality metal films (substrates), was synthesized by simply pyrolyzing [(CuBr)2(bpy)]n by adjusting the heating procedures. No capping reagent was induced to simplify the system. Since most of the research of pyrolysis of coordination polymers focuses on the relationship between the structure of precursor and sinter, the results of this paper show how the reaction conditions affect the morphology of the product and give a simple method for the synthesis of a Cu(111) flake, which has wide application in industry.