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Based on a nitrogen-rich Y-shape energetic ligand, tris(5-aminotetrazole)triazine (H3TATT), a new green solvent-free energetic metal–organic framework (EMOF) [Co(HTATT)]n, has been synthesized under hydrothermal conditions. X-ray single crystal structure analysis shows that [Co(HTATT)]n has a 3D framework structure with building units [Co1-(μ4′-HTATT)-Co1]. The thermal decomposition behavior, the kinetic parameters of the exothermic process, the calculated detonation properties and sensitivities to impact and friction stimuli of [Co(HTATT)]n were investigated. Using differential scanning calorimetry, [Co(HTATT)]n was explored as a combustion promoter to accelerate the thermal decomposition of ammonium perchlorate (AP). Experimental results indicated that [Co(HTATT)]n possesses potential application prospects in the field of greener propellants. Magnetic measurements performed on [Co(HTATT)]n with the tetrazolyl-bridged Co(II) EMOF structure display spin-glass behavior with the coexistence of spin-canting ordering below 4.0 K.

Reaction of FeCl2·4H2O, 5-bromonicotinic acid and 4,4′-bipyridine under hydrothermal conditions produced a new isomer of [(Fe iii )2Fe ii (μ3-O)(5-bromonicotinato)6]n, which represented 3D metal–organic covalent framework with trinuclear oxo-centered mixed valence iron clusters. Crystal structure of the isomer has been characterized by single crystal X-ray diffraction data and found distinct from the one for the known isomer with 2D structure.

The reaction of CuCl and NaN3 with 4,4′-azo-1,2,4-triazol-5-one (H2ZTO) under solvothermal conditions produced a new 3D heteronuclear Cu(I)-Na(I) energetic metal–organic framework (EMOF), [Cu3Na(ZTO)2]n·nCH3CN (1). Compound 1 underwent a heating–desolvation process that resulted in a new stable solvent-free EMOF, [Cu3Na(ZTO)2]n (2), with a nitrogen content of 37.22%. The heat of detonation found for compounds 1 and 2 were 1.67 kcal g−1 and 1.71 kcal g−1, respectively. Compound 2 exhibits a higher thermal stability, and is insensitive to external stimuli. The non-isothermal kinetic and apparent thermodynamic parameters for the exothermic decomposition process of 2 were determined using Kissinger's and Ozawa's methods.

Based on a flexible Y-shaped energetic ligand, tris(5-aminotetrazole)triazine (H3TATT), two new energetic coordination polymers (ECPs), {[Zn2(HTATT)2(H2O)2]·3H2O}n (1) and [PbZn(TATT)(OH)(H2O)]n (2), have been synthesized under hydrothermal conditions. X-ray single crystal structure analysis shows that both 1 and 2 are 1D chain structures. Different from 1, a large number of hydrogen bond interactions in 2 expand it into a 3D supramolecular configuration. The theoretical density and thermal stability of 2 are higher than 1. The experimental values of molar heat capacities of 1 and 2 in the temperature range of 293.15 K–368.15 K are measured by using a DSC instrument and fitted to a polynomial equation of heat capacities by the least squares method. Smoothed heat capacities and thermodynamic functions of 1 and 2 relative to the standard reference temperature 298.15 K were derived from the fitted polynomial equation. In addition, the theoretical estimation results show that 1 and 2 possess good detonation velocity and detonation pressure. Sensitivity tests indicate that 1 and 2 are insensitive to impact and friction stimuli. Furthermore, 1 and 2 were explored as combustion promoters to accelerate the thermal decomposition of RDX (1,3,5-trinitro-1,3,5-triazinane) by differential scanning calorimetry.

In this work, a new energetic coordination polymer (ECP), [Cu(HBTI)(H2O)]n (1) (H3BTI = 4,5-bistetrazole-imidazole), was synthesized by a hydrothermal method. Due to the existence of coordination water molecules in 1, however, its energy density was limited, which led to the insufficient detonation performance. To further improve its detonation performance, [Cu(H2BTI)(NO3)]n (2) was then obtained by substituting the coordinated water molecule in 1 with nitrate through the coordination substitution reaction under acidic conditions. The structures of two ECPs were respectively characterized using X-ray single-crystal diffraction, and the theoretical density of 2 (2.227 g·cm-3) was greater than 1 (1.851 g·cm-3). Thermogravimetric analyses showed that 2 has a one-step rapid weight loss process compared with the two-step slow weight loss process of 1. The theoretical calculations indicated that the detonation performances of 2 were better than those of 1. Moreover, the promotion effects of two ECPs on the combustion decomposition of ammonium perchlorate were studied using a differential scanning calorimetry method.

A new 2D MOF with unique [Co5(μ3-OH)2]8+ subunit, [Co5(μ3-OH)2(bcpt)4(bib)2] (1) (H2bcpt = 3,5-bis(3′-carboxyphenyl)-1,2,4-triazole, bib = 1,4-bis(1-imidazoly)benzene) is prepared, which not only shows weak antiferromagnetic interaction between the adjacent Co(II) ion, but also exhibits efficient electrocatalytic hydrogen evolution reaction by the integration with graphene (Gr).

A new oxo-centered, carboxylate bridged trinuclear mixed-valence iron coordination polymer has been obtained under hydrothermal conditions, [(FeIII)2FeII(μ3-O)(BNA)6]n (1). Single crystal X-ray diffraction analysis of the black crystal reveals that three iron atoms occupy the vertices of a non-equilateral triangle with the Fe┄Fe distance in the range of 3.245 A–3.343 A and are bonded by the μ3-oxo-centered and BNA− ligands. The crystal belongs to the monoclinic crystal system with a = 11.2904(6) A, b = 18.4960(11) A, c = 21.4349(12) A, β = 91.029(1), space group P21/c, GOF = 1.028, final R1 = 0.0156, wR2 [I > 2σ(I)] = 0.0405.

Two new complexes [Co3(Htrz)6(H2O)6](NO3)6·2H2O (1) and [Co3(Hdatrz)6(H2O)6](ClO4)6·4H2O (2) (Htrz = 1 H-1,2,4-triazole, Hdatrz = 3,5-diamino-1H-1,2,4-triazole) were synthesized at room temperature and characterized by elemental analysis, IR and TG-DTG and DSC. X-ray diffraction analyses. The two complexes consisted of similar linear trinuclear Co(II) units displaying 3D supramolecular architectures linked by a number of hydrogen bonding interactions. Thermal stability of the main frame of complex 2 is higher than 200 °C.

Two new Co(II) coordination polymers(CPs), namely [Co2(bpe)2(Hbppc)]n (1) and [Co3(μ3-OH)(bppc)(bpm)(H2O)]·3H2O (2) (H5bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (44·610·8)(44·62) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)]5+ units with unusual (3.46.52.6)(32.46.57.65.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system.

The reaction of silver nitrate with (1e)-N′-hydroxy-2-(1H-1,2,4-triazol-1-yl) ethanimidamide (HTE) at room temperature affords a new 3D metal-organic frameworks, {[Ag3(HTE)2(NO3)2]·NO3}n (1). Single crystal X-ray diffraction analysis reveals that the three silver metal centers are bridged by two HTE ligands and Ag-Ag strong interactions in 1. The bridges provided through the nitrogen atoms on triazole-ring and the nitrogen atoms of the ethanimidamide resulted in a trinuclear units {Ag3(HTE)2} linked metal organic framework (MOF) structure. The MOF is displaying the trinuclear units that are connected via nitrates to give a 3D network. There are free nitrates incorporated in the channels of the MOF.

A new supramolecular architecture, {[Zn(FDC)(phen)(H2O)]·0.5H2O}n (1), was obtained from mixed rigid ligands [9-fluorenone-2,7-dicarboxylic acid (H2FDC), 1,10-phenanthroline (phen)] and zinc(II) nitrate under hydrothermal reactions, which displays a charming 1D → 3D polycatenated motif based on 1D single-armed polymeric chains via powerful π π stacking interactions. In addition, the thermal stability and photoluminescence property of 1 were also investigated.

Based on the ligands tetrakis(4-carboxyphenyl)silane (TCS) and 4,4′-bipy, a novel 3D doubly interpenetrated Zn(II)-paddlewheel metal–organic framework Zn2TCS(4,4′-bipy) (1) was synthesized via facile conversion of its non-interpenetrated isomer (2) upon solvent removal at ambient temperature. It exhibits high CO2 and CH4 adsorption capacities and exceptional water stability.

The reactions of Co II or Ni II acetate with azobenzene-3,3′-dicarboxylic acid (3,3′-H2AZDB) and 1,2-bis(4-pyridyl)ethylene (bpe) afforded two isomorphic compounds [M 2(3,3′-AZDB)2(bpe)2]n (M=Co (1) and Ni (2)) under hydrothermal conditions. They were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction technique. The structures of compounds 1 and 2 have similar 3-D 3-fold interpenetrating structures in which each 3-D net displayed a 6-connected pcu network consisting of M 2+-AZDB2− layers and bpe pillars. Variable-temperature magnetic-susceptibility measurements revealed the occurrence of weak antiferromagnetic interactions between the Co(II) atoms in 1.

Based on two positional isomers of phenylenedioxydiacetate ligands and different N-containing co-ligands, six novel coordination polymers, formulated as {[Zn(o-PDOA)(bpp)]·2H2O}n (1), {[Cd(o-PDOA)(bix)]·3H2O}n (2), [Cd(m-PDOA)(bix)]n (3), [Cd(m-PDOA)(bib)]n (4), [Zn(m-PDOA)(bix)]n (5), {[Zn(m-PDOA)(bib)]·2H2O}n (6), (o/m-H2PDOA = 1,2/1,3-phenylenedioxydiacetic acid; bix = 1,4-bis(imidazol-ylmethyl)benzene; bib = 1,4-bis(1H-imidazol-1-yl)-butane; bpp = 1,3-bis(4-pyridyl)propane), have been synthesized under hydrothermal conditions. Compound 1 features a three-dimensional (3D) 2-fold interpenetrating cds topology. In 2, the (H2O)6 clusters interlink the 1D double [Cd2(o-PDOA)2(bix)2]n chains into a 3D supramolecular network. Compound 3 is a (3,5)-connected 2D layer with (42.6)(42.67.8) topology. Compound 4 exhibits a 3-fold interpenetrating pcu topological network, while, 5 is a 2D puckered meso-helical 44-sql layer built by alternately arranged right-handed and left-handed helical chains. In contrast to 1–5, compound 6 possesses a 1D loop-like chain and, interestingly, rare D4 tetrameric (H2O)4 cluster extends the chains into a 3D supramolecular framework. Moreover, the thermal stabilities and luminescent properties of compounds 1–6 have also been investigated.

In order to further design and successfully prepare for the functional metal-organic framework materials, it is essential to understand the fundamental correlations between the composition, physical properties and topology of the underlying nets. In this review, we focus on recent advances in metal-organic frameworks (MOFs) that possess more common non-zeotype 4-connected topological nets (such as sql , kag , nbo , lvt , cds , qtz , dia , lon , pts , etc.), and discuss the synthetic strategies of non-zeotype 4-connected MOFs and their related properties. In particular, we emphasize how to establish basic design principles and synthetic methodology to construct the same topological MOFs with different functions using specifically designed organic linkers.

A novel 3D entangled ZnII-coordination polymer {[Zn(abtc)0.5(btb)]·2H2O} n (1) [H4abtc = 3,3′,5,5′-azobenzenetetracarboxylic acid, btb = 1,4-bis(1,2,4-triazol-1-yl)butane] was synthesized under hydrothermal reaction conditions and characterized by elemental analysis, IR spectra, TG, PXRD and single-crystal X-ray diffraction. In compound 1, the μ4-abtc4− tectons act as the square-planar nodes to link the ZnII ions into 2D helical layers, while the secondary btb ligands further connect tetrahedral [ZnO2N2] building units into 2D motifs, resulting in a (4,4)-connected self-penetrating 86 binodal networks that can be viewed as cross-linking of two interpenetrating (3,4)-connected networks. The thermal stability and photoluminescence property of 1 were also investigated. Synthesis, structure and spectroscopic characterization of a novel (4,4)-connected self-penetrating 86 binodal coordination network. A novel 3D self-penetrating 86 binodal networks, with mixed tetrahedral and square-planar nodes, have been successfully constructed by two type of btb ligands interconnecting meso-helical [Zn2-abtc] n layers, which can be viewed as cross-linking of two interpenetrating (3,4)-connected networks. The thermogravimetric analysis and the photoluminescence properties of complex 1 were also studied.

Four coordination polymers, [Zn(o-bdc)(bth)0.5(H2O)] n (1), [Cd(o-bdc)(bth)0.5(H2O)] n (2), [Zn(m-bdc)(bth)] n (3), and [Cd(p-bdc)(bth) · (H2O)2] n (4) (where o-bdc = 1,2-benzenedicarboxylate, m-bdc = 1,3-benzenedicarboxylate, p-bdc = 1,4-benzenedicarboxylate, and bth = 1,6-bis(triazol)hexane), have been hydrothermally synthesized and structurally characterized. Both 1 and 2 are isostructural, featuring two binodal architectures: (63)(65·8) topology in terms of o-bdc and ZnII/CdII as three- and four-connected nodes. Complex 3 shows a 2-D (4,4) network with the Zn ··· Zn ··· Zn angle of 57.84°, whereas 4 exhibits planar 2-D (4,4) network. These 2-D networks of 3 and 4 are extended by supramolecular interactions, such as CH ··· π/π–π stacking and hydrogen-bonding into 3-D architecture. A structural comparison of these complexes demonstrates that the dicarboxylate building blocks with different dispositions of the carboxyl site play a key role in governing the coordination motifs as well as 3-D supramolecula...

An unprecedented 2D coordination polymer with unique (3,4)-connected self-catenated topology, arising from the parallel interlocking of 1D loop chains via shared binuclear subunits, were prepared from CdII, 5-nitroisophthalic acid and 4,4′-dipyridylamine. The thermal stability and photoluminescence property as well as the photocatalytic performance of 1 were also examined, and the results indicated that 1 shows photocatalytic activity for dye degradation under UV light.

Two flexible V-shape ligands, namely, 1,3-bis(pyridine-4-ylmethoxy)benzene (4-bpmb) and 1,3-bis(pyridine-2-ylmethoxy)benzene (2-bpmb), have been synthesized and employed for constructing eight novel coordination polymers, {[Zn(4-bpmb)(H2O)(NO3)2]·(4-bpmb)}n (1), {[Cd(4-bpmb)(H2O)(NO3)2]·(4-bpmb)}n (2), {[Hg(4-bpmb)(H2O)(NO3)2]·(4-bpmb)}n (3), {[Zn4(2-bpmb)4Cl8]·C5H5N}n (4), {[Hg(2-bpmb)Cl2]·2H2O}n (5), [Cu4(μ-CH3COO)8(2-bpmb)2]n (6), [Ag(2-bpmb)(NO3)]n (7), {[Cu(2-bpmb)(H2O)2]·(NO3)2}n (8). These complexes were characterized by elemental analyses and IR spectra and structurally determined by powder and single crystal X-ray diffraction analyses. The photoluminescence properties of complexes 1−3 are studied. The results revealed that the 4-bpmb ligands react with II B group transitional metallic nitrates to give three isostructural 1D wavelike chains (complexes 1−3), which are further decorated by equimolar 4-bpmb molecules to form the wavelike double-stranded chain structures via hydrogen bonds. In the pac...

The reactions of Cd(NO 3 ) 2 · 4H 2 O with imidazol-4,5-dicarboxylic acid and 4,4′-bipyridine under hydrothermal reaction conditions resulted in two metal–organic polymers [(H 2 O) 2 Cd(H 2 IDC) 2 ] · BPY ( 1 ) and [(H 2 O) 2 Cd 2 (HIDC) 2 BPY] ( 2 ). The compound 1 has a three-dimensional (3D) hydrogen-bonding network. The hydrogen-bonding linked 3D structure of complex 2 composed of covalent pleated sheets.

The first coordination polymer with two distinct two-dimensional layers has been synthesized and characterized [(H2O)Cu(IN)2(BPY)Cu(IN)2] 1 (IN = isonicotinate; BPY = 4, 4′-bipyridine). The entire length of the BPY molecule with “free” nitrogen cap in Cu1 layer penetrates through the parallel neighboring Cu2 layer, with half of the BPY shown above the penetrated Cu2 layer, forming a male–female paired layer network.

This account reviews Cu-containing polymeric coordination compounds synthesized under hydrothermal conditions. The rapid growth of hydrothermal synthesis of new coordination polymers is largely accredited to the developments in crystal engineering via functional network design. Both projected and unexpected framework structures have been obtained through oxidation, reduction, substitution, chemical rearrangement and regular hydrothermal reactions. New methods and reaction pathways play crucial roles in the formation of novel structures and topology under hydrothermal conditions. This review covers copper iodine-containing metal–organic coordination polymers, copper pyridylcarboxylate-containing metal–organic coordination polymers, and metastable coordination polymers with active copper open metal (OM) sites.

Two new noncentrosymmetric coordination polymers, [(H2O)2Co(BPY)(BPEN)2]·(BPEN)1.6·(BPY)0.4·2NO3·4.65H2O and [(H2O)2Ni(BPY)(BPEN)2]·(BPEN)1.6·(BPY)0.4·2NO3·4.65H2O, have been synthesized under hydrothermal conditions. The structure consists of large rectangular grid networks. The acentricities of the compounds were introduced by unbalanced inclusion species. Both 4,4′-bipyridine (BPY) and 1,2-bis(4-pyridyl)ethylene (BPEN) display pure covalent, hydrogen and bifunctional bonding modes in the structure.

In order to further design and successfully prepare for the functional metal-organic framework materials, it is essential to understand the fundamental correlations between the composition, physical properties and topology of the underlying nets. In this review, we focus on recent advances in metal-organic frameworks (MOFs) that possess more common non-zeotype 4-connected topological nets (such as sql , kag , nbo , lvt , cds , qtz , dia , lon , pts , etc.), and discuss the synthetic strategies of non-zeotype 4-connected MOFs and their related properties. In particular, we emphasize how to establish basic design principles and synthetic methodology to construct the same topological MOFs with different functions using specifically designed organic linkers.

An oxidation reaction route under hydrothermal conditions afforded a novel mixed-valent-copper coordination polymer with unprecedented mutual-face-insertion layered open-framework displaying graphite-like properties.

Two new coordination polymers, [(oxa)Fe(DPA)] (1) (DPA=2,2-dipyridylamine; oxa=oxalate) and [(oxa)Ni(DPA)] (2), were synthesized through a self-assembly chemical process under hydrothermal conditions, and characterized by single crystal structures. The CH⋯O hydrogen bonds in 1 and 2 play important roles in the crystal packing of the two new compounds.

The reactions of CoBr2 with oxalic acid and BPE (1,2-bis(4-pyridyl)ethane) or DPA (2,2′-dipyridylamine) under hydrothermal conditions resulted in projected two-dimensional coordination polymers [(C2O4)Co(BPE)]∞ and [(C2O4)Co(DPA)]∞.

Two isomorphic phases of one-dimensional coordination polymer ZnCl2(4,4′-bpy) were prepared from hydrothermal reactions of ZnCl2 and 4,4′-bipyridyl (4,4′-bpy). α-ZnCl2(4,4′-bpy) (I) crystallizes in the monoclinic space group C2/c, with a=15.821(3) A, b=5.109(1) A, c=14.612(3) A, β=110.33(3)°, V=1107.5(4) A3, Z=4. β-ZnCl2(4,4′-bpy) (II) crystallizes in the orthorhombic space group Pnma, with a=17.349(3) A, b=12.407(2) A, c=5.114(1) A, V=1100.8(3) A3, Z=4. The crystal structures of the two compounds are closely related to each other. In both phases, the Zn metal center is tetrahedrally coordinated to two terminal Cl and two bridging 4,4′-bpy. Each 4,4′-bpy acts as a bifunctional ligand and is bonded to two Zn to give rise to a Zn(4,4′-bpy) zig-zag chain. The extended Huckel (EH) calculations were performed on both structures to analyze the bonding. The solubility of the title compounds was also tested.

Two-dimensional transition-metal coordination polymers [MCl2(bpy)] (M = Fe, Co, Ni; Co/Ni, bpy = 4, 4‘-bipyridine) have been synthesized in superheated water solutions. The hydrothermal routes resulted in four compounds [FeCl2(bpy)](I), [CoCl2(bpy)](II), [NiCl2(bpy)](III), and [(Co/Ni)Cl2(bpy)](IV). Compounds I−IV are isostructural and belong to orthorhombic crystal system, space group Cmmm (No. 65). Crystal data for I: a = 11.929(2) A, b = 11.447(2) A, c = 3.638(1) A, V = 496.77(18) A3, Z = 2. Crystal data for II: a = 11.993(2) A, b = 11.374(2) A, c = 3.611(1) A, V = 492.57(18) A3, Z = 2. The structure is a noninterpenetrating two-dimensional network containing transition-metal centers octahedrally coordinated by four bridging chlorine and two bpy ligands at trans positions. The adjacent bpy ligands within a single layer are parallel to each other at a distance of 3.6 A. Spontaneous antiferromagnetic ordering was found in all compounds from the magnetic susceptibility χ(T) measurements under low fields...

By controlling stoichiometry, three Copper(I) containing coordination polymers [Cu2Cl2(bpy)] (I), [Cu2Br2(bpy)] (II), and [CuBr(bpy)] (III) (bpy = 4,4‘-bipyridine) have been synthesized in superheated water at 170 °C. The crystal structures of I and II are two-dimensional networks composed of Cu2X2 double chains bridged by 4,4‘-bpy molecules through the nitrogen sites. The structure of III is a three-dimensional interpenetrating network constructed by concatenated 2D sheets. TGA studies indicate that these compounds are thermally stable up to 220 °C.

A new family of two-dimensional metal coordination polymers with the general formula [M(ox)(bpy)] (M = Fe(II), Co(II), Ni(II), Zn(II); ox = C2O42-; bpy = 4,4‘-bipyridine) have been designed and synthesized via hydrothermal routes. Quantitative yields were obtained in all cases. The title compounds [Fe(ox)(bpy)] (I), [Co(ox)(bpy)] (II), [Ni(ox)(bpy)] (III), and [Zn(ox)(bpy)] (IV) represent the first coordination network structure constructed by bridging oxalate and 4,4‘-bpy mixed ligands. I−IV are isostructural and belong to the orthorhombic crystal system, space group Immm (No. 71). The noninterpenetrated structure contains octahedral metal centers coordinated by two oxalate and two bpy ligands to form a two-dimensional layered network. Within each layer, relatively large rectangular voids are formed by four adjacent metal centers and the ligands bonded to them. The approximate dimensions of these cavities are 4 × 7 × 10 A in the composite three-dimensional structures. Magnetic susceptibility and field-de...

A new two-dimensional coordination polymer, [Cd(NA)2], has been synthesized under hydrothermal reaction conditions. The two-dimensional networks show paired stacking arrangement and the 2-D networks are stabilized via interdigitation and π–π interactions.

Cs{sub 2}PdSe{sub 8}(1), a novel palladium polyselenide with a three-dimensional open framework structure, has been synthesized via a solvothermal reaction using ethylenediamine as solvent. Its crystal structure has been determined by single crystal X-ray diffraction. The structure belongs to the tetragonal space group I4{sub 1}/acd (No. 142), a = 14.935(2), c = 12.907(3) {angstrom}, V = 2897.0(8) {angstrom}{sup 3}, Z = 8, R{sub 1} = 0.044, and wR{sub 2} = 0.063, for 640 unique reflections. The unique three-dimensional network is composed of two {sub {infinity}}{sup 3}[Pd(Se{sub 4}){sub 2}]{sup 2{minus}} frameworks that are topologically identical and mutually insertional. Each framework is built upon by connecting the neighboring square-planar [Pd(Se{sub 4}){sub 2}]{sup 2{minus}} units to generate an infinite assembly resembling alternating right- and left-handed helices running along the c-axis. Thermal analysis (TGA) showed that compound 1 is stable up to 320 C. Optical studies performed on the powder sample of 1 suggested that the compound is a semiconductor and a band gap of 1.5 eV was estimated from the diffuse reflectance data.

Two novel two-dimensional (layered) intermetallic copper selenoantimonates Cu2SbSe3·0.5en (I) and Cu2SbSe3·en (II), have been prepared by soft solvothermal reactions of CuCl, SbCl3, and Se with A2Se (A = Na, K) in the presence of ethylenediamine. Single-crystal X-ray diffraction analyses show that both structures crystallize in the monoclinic crystal system. Compound I belongs to the P21/n (no. 14) space group with a = 6.399(1) A, b = 18.858(4) A, c = 6.786(1) A, β = 113.23(3)°, Z = 4, V = 752.5(2) A3, and II belongs to the Pn (no. 7) space group with a = 6.321(2) A, b = 11.841(2) A, c = 6.932(2) A, β = 111.59(2)°, Z = 2, V = 482.4(2) A3. Both compounds consist of Cu2SbSe3 layers separated by free ethylenediamine molecules. The intermetallic layers are very similar in I and II, but the orientations of the solvent molecules are different. Both compounds contain copper atoms of mixed-valence, Cu(I) and Cu(II), and both are semiconductors with intermediate band gaps (∼1.6 eV).

A new nitrophenyldicarboxylate-bridged tetranuclear-copper complex combined with 1,10-phenanthroline, [Cu4(nbdc)4(phen)4(H2O)4] · 2H2O, has been synthesized and characterized, and it displayed intense fluorescent emissions. The compound crystallized in triclinic crystal system, space group, P 1 ¯ , a = 10.9938(8), b = 13.9064(10), c = 13.9683(10) A, α = 99.770(1), β = 97.198(1), γ = 113.401(1)°, V = 1887.1(2) A3, Z = 2.

A unique 2-D coordination network sandwiched by alternating 1-D intra-hydrogen bonding networks has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction technique and thermal analysis. [(H2O)Mn(BN)2] (BN = bromonicotinato) crystallized in monoclinic crystal system, space group P21/c with unit cell dimensions a=10.385(1), b=10.151(1) and c=7.156(1) A, β=98.119(1)°, Z=2.

The first 1-D double-helical-chain coordination polymer, [(H2O)Cu(BPDC)] (2,2′-biphenyldicarboxylate), based upon the binuclear square pyramidal copper(II)-pair motifs has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction technique. [(H2O)Cu(BPDC)] crystallized in orthorhombic crystal system, space group Cmca with unit cell dimensions a=21.073(6) A, b=7.118(2) A and c=17.670(5) A, Z=8.

The reaction of three-dimensional (3D) CuO (tenorite) with 1,4-naphthalenedicarboxylic acid and 2,2 ′ -dipyridylamine under hydrothermal conditions produced the first 1,4-naphthalenedicarboxylate bridged coordination dimmer linked via hydrogen-bonding water molecule into a two-dimensional (2D) network structure. Instead of using simple inorganic salts, the 3D solid-state CuO was used as the copper-ion source for the reaction. The hydrogen-bonding water molecules in the network structure were completely lost below 250 °C and the dimmer was decomposed from 250 to 310 °C.

The first oxalato and isonicotinato mixed-ligand guest-inclusion open-framework coordination polymer {[(H2O)2(oxa)Zn2(IN)2]·2(H2O)} was synthesized from a chemical rearrangement of isonicotinate to oxalate under hydrothermal conditions: space group, P21/c; a = 8.302(1), b = 15.557(2), c = 7.344 (1) A, β = 94.351(1)°, U = 945.8(1) A3, Z = 2.

A novel three-dimensional nanostructured open-channel metal-organic framework polymer with inclusion of a polyiodide cluster has been synthesized via an oxidation reaction mechanism under hydrothermal conditions. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

A new three-dimensional (3-D) neutral coordination polymer, [Cd(NA)2] 1, has been synthesized under hydrothermal reaction conditions. The structure of 1 is self-assembled from binuclear square pyramidal cadmium that is in favor of non-interpenetrating open-frameworks and square pyramidal geometry of cadmium.

A new 3-D neutral metal–organic framework polymer, [Cu(NA)2] 1, has been synthesized under hydrothermal reaction conditions. The structure of 1 is self-assembled from binuclear square pyramidal copper(II) coordinated by multidentate nicotinato ligands.

The reaction of cobalt nitrate hexahydrate with 4,4′-bipyridine (BPY) under hydrothermal conditions produced a new cationic pocket-like coordination polymer built by mixed double-hydrogen-bonded and coordinated 4,4′-bipyridine rectangular-grid with inclusion species, and this material has been fabricated into metal–organic nanofibers by electrospinning.

A three-dimensional coordination polymer, [(H2O)2Cu(pdc)] 1 (pdc⊕=⊕pyridine-3,5-dicarboxylate), has been rationally designed and synthesized under hydrothermal reaction conditions. The structure is self-assembled from bifunctional pyridinecarboxylates and water molecules. Carboxylate groups in 1 contribute to both covalent and hydrogen bonds. The structure is stabilized by offset aryl–aryl face–face packing interactions.

Alternating one-dimensional serpentine ribbon and two-dimensional layer networks have been found in [Cu(DPA)CO3]·3H2O. The serpentine ribbon network consists of hydrogen-bonded pentagons formed from well-ordered water molecules, whereas the two-dimensional layer displays bifunctional 2,2′-dipyridylamine-linked zigzag inorganic chains of copper(II) carbonate.

Two novel two-dimensional (layered) intermetallic copper selenoantimonates Cu2SbSe3·0.5en (I) and Cu2SbSe3·en (II), have been prepared by soft solvothermal reactions of CuCl, SbCl3, and Se with A2Se (A = Na, K) in the presence of ethylenediamine. Single-crystal X-ray diffraction analyses show that both structures crystallize in the monoclinic crystal system. Compound I belongs to the P21/n (no. 14) space group with a = 6.399(1) A, b = 18.858(4) A, c = 6.786(1) A, β = 113.23(3)°, Z = 4, V = 752.5(2) A3, and II belongs to the Pn (no. 7) space group with a = 6.321(2) A, b = 11.841(2) A, c = 6.932(2) A, β = 111.59(2)°, Z = 2, V = 482.4(2) A3. Both compounds consist of Cu2SbSe3 layers separated by free ethylenediamine molecules. The intermetallic layers are very similar in I and II, but the orientations of the solvent molecules are different. Both compounds contain copper atoms of mixed-valence, Cu(I) and Cu(II), and both are semiconductors with intermediate band gaps (∼1.6 eV).

The first removable solid-state iodine inclusion eclipsed two-dimensional coordination polymer with an unusually stable open-channel structure has been synthesized and characterized by X-ray diffraction technique.

A novel porous framework polymer with expandable structure, over 8% volume expansion upon inclusion, has been characterized.

A simultaneous reduction of copper(II) to copper(I) by pyridinecarboxylate and the substitution of carboxylato groups by iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded a new iodine-inclusion coordination polymer [CuI(C5H3NI2)*1/2I2] 1. The synthetic studies of the substitution process produced a new supramolecular compound [IC5H3NCOOH] 2 and revealed that the catalytic properties of copper ions in redox and substitution reactions under hydrothermal conditions are attractive. Crystal data for [CuI(C5H3NI2)*1/2I2]: triclinic, space group P1; cell dimensions a = 4.216(1) A, b = 11.254(2) A, c = 12.196(2) A, alpha = 80.34(3) degrees, beta = 88.44(3) degrees, gamma = 83.10(3); V = 566.2(2) A(3), Z = 2. Crystal data for [IC(5)H(3)NCOOH]: monoclinic, space group P2(1)/c; cell dimensions a = 5.041(1) A, b = 17.313(2) A, c = 8.639(1) A, beta = 95.042(2) degrees; V = 751.02(13) A(3), Z = 4.