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Two three-dimensional supramolecular organic frameworks, [(H2bpdc)0.5(bipy)0.5] (1) and [(H3dpob)(bipy)·3H2O] (2), have been successfully constructed and structurally characterized (H2bpdc = 2,2′-biphenyldicarboxylic acid; H3dpob = 3-(2′,3′-dicarboxylphenoxy)benzonic acid; bipy = 4,4′-bipydine). 1 is driven by C–H···π hydrogen-bonded packing to three dimension. 2 origins form parallel-packed wavy chains and show π–π stacking-directed structure. After the SOFs are formed via weak noncovalent interaction, 1 and 2 show an enhancement in thermostability. The different conformations of bipy induced by weak noncovalent interactions are responsible for the huge dissimilarity of structural and luminescence behavior between them. Under the excitation of 365 nm ultraviolet light, 1 and 2 show stronger blue-white and green-white luminescent emissions in the solid state, respectively. In comparison with 2, supramolecular organic framework 1 shows superior performance in aggregation-induced emission (AIE) activity, wh...

Six novel luminescent materials In(III)-2,3-H2qldc/phen metal–organic assemblies (MOAs), namely, [In2(phen)3Cl6]·CH3CN (In1), [In2(phen)3Cl6]·CH3CN·2H2O (In2), [In2(phen)2Cl6] (In3), [In(3-qlc)2(phen)Cl] (In4), [In(3-qlc)2(2,2′-bipy)Cl]·2H2O (In5) and [In(3-qlc)3(phen)]·H2O (In6) (2,3-H2qldc = quinoline-2,3-dicarboxylic acid; 3-Hqlc = quinoline-3-carboxylic acid, which is formed from the decarboxylation reaction of 2,3-H2qldc; phen = 1,10-phenanthrolin; 2,2′-bipy = 2,2′-bipyridine) have been hydro(solvo)thermally synthesized and characterized by single-crystal X-ray diffraction, infrared (IR), elemental analysis, 1H NMR spectra, and thermogravimetric analysis (TGA). The crystal structures of In1–In6 indicate that the hydrogen bonding and π···π stacking interactions play critical roles in the formation of the extended supramolecular array. In1 displays the rare hexatomic ring 3D (4,5)-connected supramolecular architecture through twofold interpenetrating of 2D cell membrane-like structures. In2 exhibits a ...

Two mononuclear isomorphous complexes Fe(L1)2(SCN)2 (1) and Fe(L2)2(SCN)2 (2) [L1 = 2-(pyridin-3-yl)-1H-imidazo[4,5-f]1,10-phenanthroline; L2 = 2-(pyridin-4-yl)-1H-imidazo[4,5-f]1,10-phenanthroline] were obtained based on 1,10-phenanthroline derivatives. Due to the different structural distortion in the coordination geometries, 1 exhibits gradual spin transition around room temperature (T1/2 = 315 K), while 2 displays a stable high-spin state.

Ten novel metal-organic coordination polymers, [M5(μ3-OH)2(2,3-PDCO)4(H2O)4·xH2O] (2,3-PDCO = pyridine-2,3-dicarboxylic acid N-oxide, M = Mn2+ and x = 3 for 1, M = Co2+ and x = 3 for 3, M = Cd2+ and x = 1.5 for 10), [Mn(2,3-PDCO)(4,4′-bpy)(H2O)2] (2), [M2(2,3-PDCO)2(4,4′-bpy)(H2O)2·xH2O] (M = Co2+ and x = 1 for 4, M = Zn2+ and x = 0 for 7), [M(2,3-PDCO)(L)·H2O] (M = Co2+ and L = bbix (1,4-bis(benzimidazol-1-ylmethyl)-benzene) for 5, M = Zn2+ and L = bix (1,4-bis(imidazol-1-ylmethyl)-benzene) for 8), [Cu(2,3-PDCO)(4,4′-bpy)·H2O] (6), [Zn2(2,3-PDCO)2(bbi)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (9), were obtained under hydrothermal conditions and characterized structurally. The networks exhibit a variety of topologies and coordination modes at the metal centers. 1, 3, and 10 are isostructural and possess three-dimensional (3D) frameworks with penta-nuclear metal clusters as secondary building units (SBU). 5 and 7 individually exhibit a one-dimensional (1D) infinite chain and two-dimensional (2D) rectan...

Two novel three-dimensional (3D) metal−organic frameworks (MOFs) with cobalt(II) clusters as nodes and mixed bridging ligands as links, [Co4(OH)2(obbz)3(4,4‘-bpy)2](4,4‘-bpy) (obbz2- = N,N‘-oxamidobis(benzoato), 4,4‘-bpy = 4,4‘-bipyridine) (1) and [Co3(H2O)(obbz)3(4,4‘-bpy)2](H2O)2 (2), were obtained from the same reaction mixture but tuned by different hydrothermal temperatures: the 160 °C product 1 is a 3D MOF based on the novel tetranuclear cluster node [Co4(OH)2]6+, displaying a new eight-connected 364145464 topology, whereas the 140 °C product 2 is a 2-fold interpenetrating 3D MOF constructed from not only the binuclear cluster node [Co2(μ2-H2O)]4+ but also the mononuclear node Co2+, showing a distorted diamond network.

A three-dimensional (3D) Cu(II)-containing Prussian Blue analogue with two types of [Cr(CN)6]3- units, [Cu(2,2‘-dpa)]3[Cr(CN)6]2·3H2O (2,2‘-dpa = 2,2‘-dipicolylamine), was synthesized and character...

Anderson type heteropolymolybdates containing tris(alkoxo) ligands {MnMo6O18[(OCH2)3CR]2}3- (R = −CH2OH, −CH2CH3, and −NH2) have been successfully utilized as anions to generate the bis(ethylenedithio)tetrathiafulvalene (ET) radical cation salts: (ET)5{MnMo6O18[(OCH2)3CCH2OH]2} (5H2O) 1, (ET)5{MnMo6O18[(OCH2)3CCH2CH3]2}·(2CH3CN) 2, and (ET)6{MnMo6O18[(OCH2)3CNH2]2}·(2CH2Cl2) 3. Compound 1 shows a metallic conducting property, but compound 2 presents semiconducting behavior although both compounds possess β‘ ‘ phase packing of ET molecules, while ET molecules in compound 3 exhibit α‘‘‘ phase packing.

The reaction of MnCl2·4H2O and 2,5-dimethylpyrazine-dioxide (2,5-dmpdo) with various anions in H2O affords different complexes, the solid structures of which are controlled by the choice of counteranions. Reaction of MnCl2·4H2O and 2,5-dmpdo with NH4NCS yields [Mn(NCS)2(2,5-dmpdo)1.5(H2O)2]·0.5(2,5-dmpdo)·H2O (1), which contains Mn(II) dimers bridged by 2,5-dmpdo. However, with the replacement of NH4NCS with NaN3 or sodium dicyanamide (Na(dca)) in the above reaction, Mn(N3)2(2,5-dmpdo)(H2O)2 (2) or Mn(dca)2(2,5-dmpdo) (3) was isolated. Compound 2 consists of a one-dimensional zigzag chain constructed by 2,5-dmpdo bridging ligands. Compound 3 is comprised of two-dimensional layers constructed by bridging 2,5-dmpdo and dca ligands. These results unequivocally indicate that the nature of the counteranions, which play different roles in each complex, is the key factor governing the structural topologies of them. While using 2,3-dimethylpyrazine-dioxide (2,3-dmpdo) instead of 2,5-dmpdo, [Mn(dca)2(2,3-dmpdo)]·H...

A novel noncentric three-dimensional network Cd 3 (NCS) 6 (pzmo) 2 (1) (pzmo = pyrazine-monoxide) with complicated topology has been designed and synthesized based on an asymmetric ligand pzmo in aqueous solution. The second-order nonlinear optical property measurement gives a second harmonic generation efficiency, which is approximately 4.0 times larger than that of potassium dihydrogen phosphate (KDP).

A novel three-dimensional network Mn(tcm)2(bpeado) (1) (tcm = tricyanomethanide, bpeado = 1,2-bis(4-pyridyl)ethane-N,N‘-dioxide) consisting of 5-connected Mn(II) ions with a rare 46.64 topology has been synthesized; two such nets interlock to generate a 2-fold interpenetrated structure. Variable temperature magnetic susceptibility studies have shown that this compound displays weak antiferromagnetic coupling because of the long bpeado and tcm pathways. Consequently, no magnetic ordering was found.