Huijie Lu

2-Phenyl-4,5-imidazole dicarboxylate-based metal–organic frameworks assembled under hydro(solvo)thermal conditions

Four metal–organic frameworks, namely, [Cd2(μ2-HPhIDC)2(phen)2] (H3PhIDC = 2-phenyl-1H-imidazole-4,5-dicarboxylic acid, phen = 1,10-phenanthroline) (1), [Cd2(μ2-HPhIDC)2(2,2′-bipy)2] (2,2′-bipy = 2,2′-bipyridine) (2), [Pb3(μ4-PhIDC)2(H2O)] (3) and [Sr(μ2-H2PhIDC)2(H2O)4]·2H2O (4) have been synthesized under hydro(solvo)thermal conditions, and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. Both 1 and 2 are one-dimensional (1-D) infinite chains. Compound 3 features a two-dimensional (2-D) framework, in which Pb2+ ions are bridged by μ4-PhIDC3− ligands. Compound 4 possesses a three-dimensional (3-D) framework with a uninodal 4-connected net. The thermal and photoluminescence properties of polymers 1–4 have been investigated as well.

Two 3-D metal-organic frameworks constructed by 2-methyl or 2-ethyl imidazole dicarboxylates

Two polymeric frameworks, [Zn5(MIDC)2(HMIDC)2(phen)5] n (1) (H3MIDC = 2-methyl-1H-imidazole-4,5-dicarboxylic acid, phen = 1,10-phenanthroline) and {[Ca2(HEIDC)2(H2O)] · H2O} n (2) (H3EIDC = 2-ethyl-1H-imidazole-4,5-dicarboxylic acid), have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a 3-D structure constructed from 2-D layer motifs joined by µ 2-HMIDC2− or µ 3-MIDC3− ligands. Compound 2 also presents a 3-D framework, generated from 1-D chains linked by HEIDC2− ligands by two different µ5-modes. The thermal and solid-state photoluminescence properties of both the complexes have been determined.

A series of lanthanide-organic frameworks constructed by 2-methyl imidazole dicarboxylate and oxalate: synthesis, structures, and properties

Five lanthanide(III) coordination polymers with 2-methyl-1H-imidazole-4,5-dicarboxylic acid (H3MIDC) and ammonium oxalate, {[(Ln1)2(HMIDC)2(C2O4)(H2O)3] · 3H2O} n (Ln1 = Nd (1), Sm (2)), {[Eu2(HMIDC)2(C2O4)(H2O)3] · 0.5EtOH · 3H2O} n (3), {[Ce2(HMIDC)2(C2O4)(H2O)3] · EtOH · 3H2O} n (4), and {[Gd2(HMIDC)2(C2O4)(H2O)3] · MeOH · 3H2O} n (5), have been prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that 1 and 2 are isostructural, as are 3, 4, and 5. Each exhibits a 3-D open framework, which is built by a regular 2-D grid connected by HMIDC2− and Ln(III). The luminescence and thermal properties of these complexes have been investigated as well.

An unprecedented 2-D cluster polymer constructed from unique mixed-valence CuI6CuII6 subunits

A new 2-D cluster-based polymer {[Cu(I)(6)Cu(II)(6)L(6)(H(2)O)(3)(CH(3)OH)(6)].5H(2)O.3CH(3)OH}(n) (2) (H(3)L = C(6)H(5)C(O)NHC(S)NHCH(2)COOH) containing unique mixed-valence [Cu(I)(6)Cu(II)(6)L(6)] subunits was synthesized by reaction of single crystals of [Ln(2)(H(2)L)(4)(Phen)(2)(NO(3))(2)] (Ln = Pr (1a), Nd (1b) or Ho (1c)) (Phen = 1,10-phenanthroline) with copper(II) acetate in aqueous DMF. Interestingly, cation-exchanged products {[Cu(I)(6)Cu(II)(5)Zn(H(2)O)(3)(CH(3)OH)(6)].5H(2)O.3CH(3)OH}(n) (3) or {[Cu(I)(6)Cu(II)(4)Co(2)(H(2)O)(3)(CH(3)OH)(6)].5H(2)O.3CH(3)OH}(n) (4) were obtained from single crystals of and the appropriate M(NO(3))(2) (M = Zn or Co) in H(2)O.

Synthesis and crystal structure of yttrium(III) and lanthanide(III) complexes with a new terpyridine-like ligand 2,4-bis(3,5-dimethylpyrazol-1-yl)- 6-diethylamino-1,3,5-triazine

A new planar aromatic tridentate terpyridine-like ligand, 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylamino-1,3,5-triazine (L), has been synthesized and the structures of its complexes [YL(NO3)3] (1) and [LnL(NO3)3(H2O)]L [Ln = La (2), Ce (3), Pr (4), Nd (5), Eu (6)] have been determined by X-ray crystal structural analysis. The structures of the five lanthanoid complexes are isomorphous and isostructural but different from the crystal structure of the yttrium complex [YL(NO3)3]. The latter shows a nine-coordinate metal center whereas the crystal structure of the lanthanoid complexes [LnL(NO3)3(H2O)]L show a 10-coordinate metal center. The π–π stacking and hydrogen bonding between the coordinated and uncoordinated L molecules sensitized the Ln luminescence. The thermal behavior of the ligand and its complexes is discussed.

Self‐Assembly of 1,4‐Bis(1‐benzimidazolylmethyl)benzene with Cd(II) and Zn(II) Cations: Synthesis and Crystal Structures of a 2‐D Coordination Polymer and a 3‐D Supramolecular Complex

A novel coordination polymer, [CdCl2(bbmb)2]n and a new supramolecular complex, [H2(bbmb)ZnCl4] · H2O, [bbmb=1,4‐bis(1‐benzimidazolylmethyl)benzene] were obtained. X‐ray single crystal diffraction analysis shows that [CdCl2(bbmb)2]n exhibits a distorted octahedron and is a two‐dimensional network. Its solid‐state structure exhibits a layered packing mode. The supramolecular complex [H2(bbmb)ZnCl4] · H2O shows that the zinc(II) atom is coordinated by four chlorine ions and connected by H‐bonding with protonated bbmb and H2O forms a 3D supramolecular complex. The N H · · · O and O H · · · Cl hydrogen bonds play important roles in the crystal packing of the complexes. We are very thankful for financial support from the National Natural Science Foundation of China (No. 20171040) and the Natural Science Foundation of Henan Educational Department (No. 20011500021).

Synthesis, Crystal Structure, and Magnetic Properties of a Gd(III) Dimer Bearing Thourea-based Carboxylate Ligand

Treatment of two kinds of ligands, 2-(3-benzoylthioureido) ethanoic acid (H3L) and 1,10-phenanthroline (phen) with Gd(NO3)3 in solution, resulted in a Gd(III) dimer, {[Gd2(μ2-η2H2L)2(μ2-H2L)2(phen)2(NO3)2]·CH3OH} (1). Its crystal structure has been characterized by single X-ray determination. Also, thermostability and magnetic properties of the dimer have been researched. The results indicate that there exists antiferromagnetic coupling between the neighboring Gd(III) ions.

Synthesis and crystal structure of a new zinc diphosphonate

A new zinc diphosphonate [NH3CH(CH3)CH2NH3]2Zn2(edbbp)2(HNO3)2·4H2O [eddbp = O3PCH(Ph)NH(CH2)2NHCH(Ph)PO3] was hydrothermally synthesized with Zn(NO3)2·6H2O, ethane-1,2-diamino-N,N′-bis(benzylphosphonic acid) (H4edbbp) and 1,2-propyldiamine. It consists of a centro-symmetric dimeric unit [Zn2(edbbp)2], in which each zinc ion adopts a distorted square-pyramidal coordination geometry. Hydrogen bonds formed between phosphonate groups and protonated 1,2-propyldiamine molecules link the dimeric units into one-dimensional chains. The doubly protonated 1,2-propyldiamine molecules serve not only as charge compensating counter ions, but also as bridging groups. Hydrogen-bonding interactions among the phosphonate oxygen atoms, water molecules, nitric acid molecules and protonated 1,2-propyldiamine result in the formation of a three-dimensional supramolecular network.

Synthesis, Crystal Structure, Fluorescence, and Thermal Properties of a Novel Copper(II) Dimeric Complex

One novel dimeric complex [Cu 2 (L) 2 (μ 2 -L) 2 (CH 3 OH) 6 ] has been prepared by the reaction of organic ligand 3-(4-carboxyphenylhydrazono) pentane-2,4-dione (HL) with copper(II) ion in solution. It is a binuclear complex, in which two Cu(II) ions are bridged by two carboxyates from two L−. It was characterized by elemental analysis, IR and single X-ray determinations. Also, reaction conditions, thermostability, and fluorescent properties of the complex were researched.