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Metalation of metal–organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal–organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure– property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well. [ABSTRACT FROM AUTHOR]

Rechargeable aqueous zinc-ion batteries (ZIBs) are highly promising energy storage devices due to their advantages of high energy density, low cost, environmental friendliness, and excellent safety. Investigation of advanced cathode materials featuring high capacity is desired for their applications in high-capacity ZIBs. In this study, a porous N-doped carbon-coated manganese oxide/zinc manganate (MZM@N-C) composite was successfully prepared as an advanced cathode material for aqueous ZIBs. The MZM@N-C cathode demonstrated a superior specific capacity of 772.8 mA h g-1 at 50 mA g-1 and maintained a high specific capacity of 205 mA h g-1 after 300 cycles at a high current density of 500 mA g-1. As compared to the unmodified MnOx cathode, MZM@N-C has a higher reversible capacity and cycling stability which could be assigned to the robust one-dimensional (1D) structure and the synergistic effect of MZM@N-C, providing instructive insight into the design of high-capacity manganese-based cathodes for rechargeable aqueous ZIBs. Furthermore, a soft-pack battery was assembled using the MZM@N-C cathode, demonstrating its potential applications in various devices. [ABSTRACT FROM AUTHOR]

Eight cobalt and nickel clusters with the formulae [Co4(μ4-O)(MBT)5(μ2-Piv)] (1), [Ni3(MBT)2(L1)2(OCH3)2] (2), [Ni4(μ3-S)(µ3-S2)(MBT)2(L2)] (3), [Ni4(L3)4] (4), [Ni6(μ4-S)3(MBT)6]·(C2H5OH)2 (5), H[Co4(μ4-O)(HMBI)6]·(NO3)(TEA)0.5(CH3OH)2(H2O) (6), [Ni2(HMBI)4]·(CH3OH)2 (7), and [Ni5(MBI)2(HMBI)4(OCH3)2]·(CH3OH)3(H2O)2 (8) (HPiv = pivalic acid, HL1 = 2-disulfanylbenzo[d]thiazole, H2L2 = (Z)-2-((2-mercaptophenyl)imino)benzo[d]thiazole-3(2H)-thiol, H2L3 = (Z)-2-(benzo[d]thiazol-2(3H)-ylideneamino)benzenethiol, TEA = triethylamine) have been solvothermally prepared via assembling distinct metal resource and thiol-containing ligands 2-mercaptobenzothiazole (HMBT)/2-mercaptobenzimidazole (H2MBI). Complexes 1 and 6 are tetrahedral cobalt clusters. Complex 2 features linear arrangement of nickel ions. Complexes 3 and 4 are tetranuclear nickel clusters with the butterfly and square shape, respectively. Complex 5 displays a trigonal prism geometry. Complexes 7 and 8 exhibit paddle-wheel and trigonal bipyramidal geometry, respectively. The starting ligand HMBT undergoes in situ ligand transformation in the formation of the nickel clusters, and the new generated inorganic ligands (S2- and S22-) and organic ligands (HL1, H2L2 and H2L3) were captured within the metallic cores. Magnetic studies indicate that complexes 1 and 6 show dominating antiferromagnetic couplings and that spin frustration exists in 6. [ABSTRACT FROM AUTHOR]

Two CuII-based MOFs have been constructed by synergistic assembly involving the mixed-ligand synthetic strategy and the solvent effect. Compound 1 is a 3D structure and represents a cds topology, while compound 2 displays a rare structure built by three distinct {Cu4} clusters as SBUs. Moreover, the magnetic properties of 2 have been thoroughly investigated. [ABSTRACT FROM AUTHOR]

An in situ doping strategy was successfully applied to tune the magnetic behaviour and induce fluorescence signal mutation of a spindle heptanuclear zinc cluster-based MOF, by only modifying its structural composition. The CoII-doped ZnII-MTV-M'MOF exhibits canted antiferromagnetism and weaker fluorescence properties. [ABSTRACT FROM AUTHOR]

Solvent induced structural diversities from a cup-shaped Co8 cluster (1) in methanol to a Co8 cluster-based co-crystal chain (2) in ethanol/n-propanol and a Co8 cluster-based chain (3) in n-butanol under the same stoichiometric ratio of reactants have been reported. In situ ligand conversion has taken place and the new ligand is captured within the metallic core. Magnetic analyses indicate that theses complexes exhibit distinct magnetic behaviours at low temperature. [ABSTRACT FROM AUTHOR]

As a continuation of the study on using the tetrazolate ligands to construct coordination polymers, two isomorphous 3D coordination polymers built on Δ-chain topological rod-shaped SBUs have been synthesized with formulae [M2(μ3-OH)L1L2]n(5-amino-1H-tetrazole (HL1), 2,3-pyrazinedicarboxylic acid (H2L2) and different 3d spin carriers (M = MnII, 1and CoII, 2)). The SBU consists of corner-sharing [M3(μ3-OH)] isosceles triangle motifs with mixed multiple (μ4-tetrazolyl, μ3-OH, syn-syncarboxylate) bridges. The SBUs were further linked by syn-anticarboxylates to form the sra net. Spin-competing was observed in the MnIIcompound, whereas the CoIIcompound exhibits spin-canting. [ABSTRACT FROM AUTHOR]

An Fe-based MOF has been constructed from a paddle-wheel-like dimeric Fe-cluster and a rod-shaped sinusoidal-like Fe-chain as two distinct secondary building units. Topological analyses indicate that this compound is a tetranodal (3,3,4,8)-connected net, which represents a new structural topology in MOFs. Moreover, the magnetic properties of 1have been thoroughly investigated. [ABSTRACT FROM AUTHOR]

Five new coordination polymers, namely, [Cd4(L1)2(DPP)2(DMF)2(SO4)2]∞(1), [Zn2(L1)(DPP)2Cl2]∞(2), [Cd(L2)(DPP)]∞(3), [Zn(L2)(DPP)]∞(4) and {[Cd2(L2)Cl4][(CH3)2NH2]2}∞(5), (DPP = 1,3-di(4-pyridyl)propane and DMF = N,N-dimethylformamide), were prepared by solvothermal reactions of anthracene-9,10-dicarboxylic acid (H2L1) or anthracene-1,5-dicarboxylic acid (H2L2) with CdIIor ZnIIions, and were structurally characterized by IR, elemental analysis, XRPD and single crystal X-ray diffraction. Complex 1consists of a three-dimensional (3D) network with bcu(CsCl-type) topology assembled by pillar ligands L12−, DPP and CdIIions and has one-dimensional (1D) channels running along the a-axis. In the case of complex 2, the CdIIand SO42−ions are replaced by ZnIIand Cl−, resulting in a 1D ladder chain. Complexes 3and 4are made up of longer pillars, H2L2instead of H2L1, and have similar 3D four-fold interpenetrating diamond frameworks. And complex 5forms a two-dimensional (2D) (32.62.72) kagóme structure after taking out the longer pillar DPP. Moreover, the luminescence properties of all the complexes and the corresponding ligands in the solid state at room temperature have been investigated. [ABSTRACT FROM AUTHOR]

In our efforts to construct new metal–organic frameworks (MOFs) with open frameworks, three new metal oxalates, a 2D layered zinc oxalate [Co(en)3][Zn4(ox)7]0.5·5H2O (1), a 2D saw-tooth layered manganese oxalate [Co(dien)2][Mn4(ox)7]0.5·6H2O (2), and 3D open-framework cadmium oxalate [Co(dien)2][Cd4(H2O)2(ox)7]0.5·4.5H2O (3), have been synthesized under hydrothermal conditions by using Co(en)3Cl3or Co(dien)2Cl3as template. Compared to the previously reported oxalate compounds that possess only medium sized 12-ring channels, the three open-framework oxalates exhibit larger channels, 16- and 20-ring channels. Compound 1is a layered structure with large elliptical 20-ring channels linked by ten ZnO6and ten oxalates. Compound 2exhibits a 2D saw-tooth sheet structure with 20-membered corrugated rings, and also presents an elliptical 16-ring aperture along [101] direction. Interestingly, compound 3presents a 3D open framework, and Cd polyhedra and oxalate units alternate to form a 2D channel system that contains 12- and 20-ring channels, and it exhibits an unprecedented 3,4-connected mbc topology. Pairs of Co(iii) complexes with opposite chirality are encapsulated inside the large channels as template. Our results suggest that using metal complexes as templates should be an effective strategy to construct MOFs. [ABSTRACT FROM AUTHOR]

Two new azido-CoIIcomplexes with pyrazine carboxylato ligands, [Co(N3)(L)·H2O]n(L= pyrazine-2-carboxylato) (1) and [CoNa(N3)2(L)]n(2), have been obtained by carefully tuning the CoII : N3−ratio. Here we present the structural and magnetic characterization of these new species. Modulation of the coordination environment of CoIIleads to a variation of the magnetic properties of the obtained compounds. Complex 1exhibits ferromagnetically coupled [Co2] units that form the rungs of the ladder with a nearly negligible coupling between these units, while complex 2is a 2D arrangement of 1D CoIIsingle-chain magnets. [ABSTRACT FROM AUTHOR]

In our efforts to continuously explore the influence of ligands with larger conjugated π-systems on the related structures and properties of their complexes, four CdIIcomplexes with anthracene-9,10-dicarboxylate (L) and relevant auxiliary ligands were synthesized and characterized: {[Cd2(L)2(bipy)(H2O)2](C2H5OH)0.5(H2O)2.25}∞(1), Cd2(L)(HL)2(phen)4(2), {[Cd2(L)1.5(Hpypz)4](L)0.5}∞(3), and {[Cd(L)2](H2daco)(C2H5OH)2(H2O)}∞(4) (bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline, Hpypz = 3-(2-pyridyl)pyrazole, and daco = 1,5-diazacyclooctane). Structural analyses show that complex 1has a three-dimensional (3D) structure with a Schläfli symbol of (6·82)2(6·85). Complexes 2and 3take dinuclear and two-dimensional (2D) structures, respectively, due to the introduction of different 2,2′-bipyridyl-like chelating ligands, phen for 2and Hpypz for 3. Complex 4possesses another three-dimensional (3D) two-fold interpenetrating diamondoid network by introducing daco as an auxiliary co-ligand. The present results indicate that the natures of the auxiliary ligands have important effects on the formation of the final structures of such complexes. Moreover, the luminescent properties of complexes 1–4and the corresponding ligands have also been investigated in detail. [ABSTRACT FROM AUTHOR]

Azido has been one of the well used bridging ligands in the construction of magnetic molecule materials, which has stimulated considerable interest in magnetochemistry. This tutorial reviewis concentrated on the study of azido metal compounds with their magnetochemistry and consists of eight main sections. The first section offers an introduction to azido complexes and some important results obtained from magneto–structural correlation in azido complexes which will be referred to in the following sections. The next six sections give overviews of azido-mediated ferromagnets, ferrimagnets, canted (weak) ferromagnets, antiferromagnets, single molecule magnets (SMMs) and single chain magnets (SCMs), and metamagnets. The last section is the conclusion and gives a perspective of azido-mediated magnets. [ABSTRACT FROM AUTHOR]

In our efforts to tune the structures of AgIcomplexes by ligand modification, six structurally related ligands: 1,2-bis(triazol-1-ylmethyl)benzene (L1), 1,3-bis(triazol-1-ylmethyl)benzene (L2), 1,4-bis(triazol-1-ylmethyl)benzene (L3), 1,3,5-tri(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (L4), 1,4-bis[3-(2-pyridyl)-pyrazol-1-ylmethyl]naphthalene (L5), and 9,10-bis(benzimidazol-1-ylmethyl)anthracene (L6) have been designed and used to react with AgIsalts to form six new complexes: {[Ag2(L1)2](BF4)2(H2O)} (1), [Ag2(L2)(NO3)2]n(2), [Ag(L3)(NO3)]n(3), {[Ag3(L4)2](SiF6)1.5(H2O)3.5} (4), {[Ag2(L5)2](NO3)2(H2O)} (5), and {[Ag2(L6)2](NO3)2(CH3OH)2} (6). All the complexes have been structurally characterized by IR and X-ray diffraction. Structural analyses show that complexes 1, 5, and 6possess dinuclear structures, which extend to infinite coordination networks linked by AgN, C–HO, or π–π weak interactions. 2is a 3D chiral coordination polymer with (10,3)-a topology, and 4forms a trinuclear cage structure, which further connected by AgAg weak interactions to form a 1D supramolecule, while 3exhibits an infinite 1D chain structure. The structures of complexes 1–6span from dinuclear, trinuclear, 1D, to 3D network, which indicates that ligands play important roles in the formation of such coordination architectures. Furthermore, the CD spectrum, thermal, and fluorescent properties of the chiral complex 2have been investigated in the solid state. [ABSTRACT FROM AUTHOR]

Three new quinoxaline-based ligands with N,S-bidentate chelating sites, 2,3-bis(n-propylthiomethyl)quinoxaline (L1), 2,3-bis(tert-butylthiomethyl)quinoxaline (L2) and 2,3-bis[(o-aminophenyl)thiomethyl]quinoxaline (L3) have been synthesized and their coordination behavior with Ag(I) was studied. Four Ag(I) complexes varying from 0D to 3D have been obtained by these structurally related ligands with AgX (X = ClO4−, NO3−). Single crystal X-ray diffraction analyses show that the structures of 1and 2are directed by the counter-anions used in such a system: the reaction of L1with AgClO4yielded a tetranuclear molecular cage {[AgL1](ClO4)}4(1), while using AgNO3instead led to the formation of a 2D layer framework with ππ stacking {[Ag2L1(NO3)2](H2O)0.5}n(2). When L2was used instead of L1to react with AgNO3, a non-centrosymmetric 3D network with (82.9)2(82.9.10) topology [Ag3L2(NO3)3]n(3) was obtained, and L3instead of L1to react with AgClO4, a 1D chain with AgAg interaction {[Ag2L3(DMF)](ClO4)2(H2O)}n(4) was formed. The structural differences between 2and 3, 1and 4, respectively, clearly show the important effect of the terminal groups of ligands on the structural modulation in such coordination architectures. Moreover, there are two coordination modes of S atoms in 1–4: one is µ2-bridging (in 2and 3), and the other is a mono-coordination (in 1and 4). In addition, the luminescence properties of these compounds have also been studied in solid state at room temperature. [ABSTRACT FROM AUTHOR]

A new 3D porous NiII-azido complex has been synthesized and characterized and exhibits guest sorption properties explored by single-crystal to single-crystal transformations and linear ferromagnetic chains held together by a Ni–isonicotinate framework. [ABSTRACT FROM AUTHOR]

Four novel AgI coordination complexes with azole heterocycle ligands bearing acetic acid group, [AgL1]n (1), [Ag(L2HL2)]n (2), [AgL3]n (3) and [Ag(L4)]n (4) (here, HL1 = 1H-imidazole-1-acetic acid, HL2 = 1H-benzimidazole-1-acetic acid, HL3 = 1H-1,2,4-triazole-1-acetic acid, HL4 = 1H-benzotriazole-1-acetic acid), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Structural analyses show that complex 1 possesses a two-dimensional structure, which contains silver chains formed by weak Ag–Ag interactions, and 2 consists of neutral chains connected by weak bonds (O⋯H⋯O), while 3 and 4 have a three-dimensional network and a one-dimensional chain structure, respectively. It is interesting that in 1 there exist Ag–Ag interactions with a separation of 3.156 Å, which play an important role in the formation of the complex. Furthermore, the conductivity of 1 was studied in the powder state. [ABSTRACT FROM AUTHOR]

To systematically investigate the influence of ligands with a large conjugated π-system on the structures and properties of their complexes, we synthesized seven ZnII complexes with two anthracene-based carboxylic ligands, anthracene-9-carboxylic acid (HL1) and anthracene-9,10-dicarboxylic acid (H2L2), and sometimes incorporating different auxiliary ligands, {[Zn(L1)2(H2O)2](H2O)}∞ (1), [Zn5(μ3-OH)2(L1)8(2,2′-bipy)2] (2), Zn2(L1)4(phen)2(μ-H2O) (3), {[Zn(L1)2(4,4′-bipy)(CH3OH)2]}∞ (4), {[Zn(L2)2](Hdmpy)2(H2O)2}∞ (5), {[Zn2(L2)(2,2′-bipy)4](HL2)2}∞ (6) and {[Zn2(L2)(pypz)2(Hpypz)2]}∞ (7) (2,2′-bipy = 2,2′-bipyridine, phen = 1,10′-phenanthroline, Hpypz = 3-(2-pyridyl)pyrazole, 4,4′-bipy = 4,4′-bipyridine and Hdmpy = protonated 2,6-dimethylpyridine), which were characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. 1 has a one-dimensional (1-D) chain structure, whereas 2 exhibits a new pentanuclear cluster structure because of the introduction of a chelating 2,2′-bipy ligand. 3 and 4 take dinuclear and 1-D structures, respectively, by incorporating the auxiliary ligands phen and 4,4′-bipy. 5 is a three-dimensional (3-D) twofold interpenetrating diamondoid framework showing an open channel. 6 and 7 possess the corresponding chain structures containing Zn2 units as nodes by introducing Hpypz and 4,4′-bipy auxiliary ligands, respectively. These results indicate that the nature of ligands and auxiliary ligands has an important effect on the structural topologies of such complexes. Moreover, the luminescent properties of the corresponding complexes and ligands have been briefly investigated. [ABSTRACT FROM AUTHOR]

The influence of the nature of metal ions and reaction conditions on the formation of group IIB metal coordination architectures of a tetrazole ligand, 2-(1H-tetrazol-5-yl)pyrazine (HL), and the luminescent properties of some complexes have been investigated. At room temperature, the reactions of Zn(NO3)2∙6H2O (or ZnCl2) and Cd(NO3)2∙6H2O with HL gave rise to two reported complexes, [M(L)2(H2O)2] (1 and 2, Acta Crystallogr., Sect. C, 2006, 62, m614; Acta Crystallogr., Sect. E, 2006, 62, m2841), respectively. However, under hydrothermal conditions, the same reactions yield 1 and another complex, {[Cd2(L)4](H2O)0.25}n (3), respectively. In both preparation conditions mentioned above, the HL ligand reacts with Hg(OAc)2 (or HgBr2) to give complexes, [Hg(L)2]n (4), [Hg(L)2]n (5) and [Hg(L)Br]n (6) with different structures. 1 and 2 have a similar mononuclear structure and in the crystal structure such molecules are further assembled together to form a 3-D α-Pt topological framework with O–H⋯N hydrogen bonds. 4 possesses a 1-D chain structure, in which the Cd(ii) center is six-coordinated, with all coordination sites being occupied by N atoms of the ligands. Furthermore, such chains are interlinked viaπ⋯π interactions to form a 3-D framework. 4 has a 2-D (6,3) topological structure, in which the Hg(ii) center is six-coordinated to six N atoms of L, and the L ligand takes a chelating-bridging mode similar to that in 3. 5 has a 2-D (4,4) topological layer structure with the metal center being six-coordinated, and the six coordination sites are held by N atoms from four L ligands, taking different coordination modes. Moreover, such planes are generated to form a 3-D structure via two kinds of π⋯π interactions. 6 is a 2-D layer with the Hg(ii) coordinating to a Br atom and three N atoms of three tetrazole rings from different L ligands. This result shows that the metal ions and reaction conditions have significant influence on the group IIB metal complexes of this multifunctional ligand, and the intramolecular/intermolecular weak interactions are likely to play important roles in the formation of such complexes, especially linking the discrete subunits or low-dimensional entities into high-dimensional frameworks. In addition, the luminescent studies of HL and 1, 2, 3 and 6 indicate that they display blue emissions with different densities in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

Seven new d10 metal coordination polymers with isomeric benzenedicarboxylates and 3-(2-pyridyl)pyrazole ligands, [Zn2L2(1,2-BDC)(H2O)]n (1), {[Cd2(HL)2(1,2-BDC)2]·H2O}n (2), [Cd(HL)(1,2-BDC)(H2O)]n (3), [Zn(HL)(1,3-BDC)(H2O)·3H2O]n (4), [Cd2L2(1,3-BDC)(H2O)]n (5), [Zn(HL)2(1,4-BDC)]n (6) and [Cd(HL)2(1,4-BDC)]n (7) (BDC = benzenedicarboxylate, HL = 3-(2-pyridyl)pyrazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that each complex takes a different one-dimensional (1D) chain structure. In 1–7, the BDCs act as bridging ligands, exhibiting rich coordination modes to link metal ions. The three BDC isomers exhibit different coordination modes: µ1-η1:η1/µ3-η2:η1, µ3-η1:η2/µ3-η2:η1, µ2-η1:η1/µ1-η1:η0 and µ1-η1:η1/µ1-η1:η0 for 1,2-BDC, µ1-η1:η1/µ1-η1:η0 and µ1-η1:η0/µ2-η2:η1 for 1,3-BDC, and µ1-η1:η0/µ1-η0:η1, µ1-η1:η0/µ1-η1:η0 and µ1-η1:η1/µ1-η1:η1 for 1,4-BDC, respectively. In these complexes, HL acts as a simple bidentate chelate ligand (in 2, 3, 4, 6 and 7), similar to 2,2′-bipyridine, or as a tridentate chelate-bridging ligand (in 1 and 5) via deprotonation of the pyrazolyl NH group and coordination of the pyrazolyl N atom to a second metal ion. The structural differences indicate that the backbone of such dicarboxylate ligands plays an important role in governing the structures of such metal–organic coordination architectures, and the chelating bipyridyl-like ligand HL leads to the formation of these coordination polymers with one-dimensional structures by occupying the coordination sites of metal ions. Moreover, the photoluminescent properties of complexes 1–7 were also studied in the solid-state at room temperature. [ABSTRACT FROM AUTHOR]

Five new Zn(ii) metal–organic coordination polymers, [Zn2(L1)2(Dpq)2]·H2O (1), [Zn(L2)(Dpq)(H2O)] (2), [Zn(L3)(Dpq)(H2O)]2 (3), [Zn(Dpdq)(L3)] (4) and [Zn(Dpdq)(L4)]·H2O (5) (Dpq = dipyrido[3,2-d∶2′,3′-f]quinoxaline, Dpdq = 2,3-di-2-pyridylquinoxaline, H2L1 = benzene-1,2-dicarboxylic acid, H2L2 = benzene-1,3-dicarboxylic acid, H2L3 = benzene-1,4-dicarboxylic acid, H2L4 = biphenyl-4,4′-dicarboxylic acid), have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analyses show that complexes 1–4 possess chain structures which are further assembled to form four three-dimensional (3-D) frameworks by π–π stacking and/or hydrogen-bonding interactions, while a similar chain of 5 has a two-dimensional (2-D) network packed by π–π stacking and hydrogen-bonding interactions. In 1–3, the Dpq ligand takes a chelating coordination mode while the other two nitrogen atoms did not coordinate to the Zn(ii) ions. In 4 and 5, the Dpdq ligands have two coordination modes. The structural differences of the benzenedicarboxylate ligands and N-containing rigid/flexible chelating ligands have a great influence on the geometries of the corresponding complexes. This result also shows that intramolecular/intermolecular weak interactions play an important role in the formation of supramolecular networks, especially in linking low-dimensional entities into high-dimensional supramolecular frameworks. In addition, complexes 1 and 3–5 exhibit blue emission in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

In our continuing efforts to investigate functional metal-organic coordination architectures, a benzimidazole-based rigid ligand, 9,10-bis(N-benzimidazolyl)anthracene (L), has been designed and used to react with CuI, AgI, CdII, MnII salts, giving rise to five new metal-organic coordination architectures, [CuLI]2·2CHCl3·H2O (1), [CdL2(NO3)2]·4C2H5OH (2), [AgL(BF4)]·3CHCl3 (3), [AgL(NO3)]·2CHCl3 (4) and [MnL2Cl2]·2CHCl3 (5), which were characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. In 1, the CuI ion takes tetrahedral coordination geometry, and the rigid ligands bridge two dinuclear [Cu2I2] units to form a two-dimensional (2-D) layer. 2 and 5 show 2-D network structure with (4,4) topology in which the metal ions have octahedral coordination geometry. 3 and 4 display one-dimensional (1-D) chain structures, but show different crystal packing modes due to the effect of anions. These results indicate that the nature of ligand, metal coordination geometry and counter-anions have important effects on the structural topologies of such complexes. Furthermore, complexes 1–4 display strong blue emissions in solid state at room temperature. [ABSTRACT FROM AUTHOR]

In our continuous efforts to explore the effects of metal ions, ligand structures, counter-anions on the structure and properties of metal–organic complexes, six new d10 metal coordination polymers with an anthracene-triazole ligand, 9,10-bis(triazol-1-ylmethyl)anthracene (L), {[Cu(L)I]}∞(1), {[Ag(L)(BF4)]}∞(2), {[Zn(L)(NO3)2]}∞(3), {[Zn(L)(CH3OH)2(ClO4)2(H2O)]}∞(4), {[Cd(L)(CH3OH)2(ClO4)2(H2O)]}∞(5) and {[Hg(L)(Br2)]}∞(6), were synthesized and structurally characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. 1–3 and 6 have similar one-dimensional (1-D) chain structures in which 1, 3 and 6 were further linked into infinite two-dimensional (2-D) sheets by inter-chain C–H⋯I, π⋯π or C–H⋯Br weak interactions, respectively, while 2 was extended into three-dimensional (3-D) supramolecular network by Ag⋯F and Ag⋯N weak interactions. 4 and 5 possess similar (4,4) 2-D sheet structure containing only one type of rhombic grid, and the Zn/Cd atoms are regarded as the four-connected nodes and the ligand as bridges. Obviously, the structural differences among them are attributable to the different metal ions and counter anions. In 1–6, L adopts a trans-gauche conformation with the shortest N⋯N distance between the two N donors. Furthermore, the fluorescent properties of 1–6 and ligand L have been investigated. [ABSTRACT FROM AUTHOR]

A sixfold interpenetrated microporous MOF has been constructed from a heterometallic tetranuclear cluster. The framework contains two types of 1D micro-channels along different directions. Moreover, this compound exhibits high selective gas sorption for H2over N2. [ABSTRACT FROM AUTHOR]

A new 2D coordination polymer with an azide-bridged 1D homospin chain is synthesized, which shows slow magnetic relaxation and step hysteresis loop, and is ascribed to be a typical Ising-type single-chain magnet. [ABSTRACT FROM AUTHOR]

The enantiomers of complex 1 (1a and 1b) have been obtained by spontaneous resolution upon crystallization in the absence of a chiral source. The enantiomeric nature of 1a and 1b was confirmed by circular dichroism (CD) spectra and theoretical investigation. [ABSTRACT FROM AUTHOR]

Three new 1D lanthanide-azido complexes, [Ln2(N3)(isonic)2- (OH)3(Hisonic)(H2O)]n (Ln = GdIII, EuIII and SmIII), were synthesized by hydrothermal reaction and their magnetic properties were studied. [ABSTRACT FROM AUTHOR]

An azido–metal–1,2,4-triazolate coordination polymer, [Cu(trz)(N3)]n (trz = 1,2,4-triazolate) was synthesized using hydrothermal methods; the complex has a rare three-dimensional non-interpenetrated utp or (10,3)-d topological network structure and exhibits spin-canted antiferromagnetism at low temperature. [ABSTRACT FROM AUTHOR]

The in situ solvothermal reaction of 3,4-dicyano-1,2,5-thiadiazole with MCl2 (M = Co, Ni) and NaOH afforded two isomorphous complexes, [M2(L)2(H2O)2]n (L = 2,1,3-thiadiazole-4,5-dicarboxylate), which exhibit a rare non-interpenetrated (10,3)-d (utp) network topology and interesting magnetic behaviors: spin-canted antiferromagnetism for the CoII complex, but simple antiferromagnetic coupling for the NiII. [ABSTRACT FROM AUTHOR]

The in situ solvothermal reaction of 9,10-dicyanoanthracene and ZnCl2/NaN3 gave the complex, {[Zn7(OH)8(DTA)3]·H2O}n (1) (DTA2− = 9,10-ditetrazolateanthracene), which presents a pcu-type topological framework formed by DTA2− bridging unprecedented heptanuclear spindle [Zn7(OH)8]6+ clusters as SBUs, and exhibits strong luminescent emission with long lifetime. [ABSTRACT FROM AUTHOR]