De-Yun Ma

Synthesis, structural characterization, and properties of an entangled metal–organic framework based on a flexible dicarboxylate and a rigid N-donor

Self-assembly of manganese acetate with 1,3-bis(4-carboxy-phenoxy)propane (H2bcp) and 1,2-bis(4-pyridyl)ethene (bpe) under solvothermal conditions yielded a polymer {[Mn2(bcp)2(bpe)(DMF)]} n (1), which shows 2-D → 3-D inclined interpenetration with polyrotaxane character. The magnetic behavior of 1 shows antiferromagnetic exchange between Mn magnetic centers.

A hydrostable anionic zinc-organic framework carrier with a bcu topology for drug delivery

A hydrostable anionic porous drug carrier MOF with a bcu topology constructed from trinuclear clusters, [(Me2NH2)2Zn3(fdc)4]n·DMA (1) (fdc = 2,5-furandicarboxylate, DMA = dimethylacetamide), was synthesized and structurally characterized. TGA, PXRD, and water vapor sorption results show high thermal and water stability for the framework. 1 exhibits a 3D framework with rectangular channels of 10.0 × 7.7 and 6.1 × 7.8 A2 along the b axis. Desolvated 1 adsorbs around 17.2 wt% 5-fluorouracil and the cumulative release value of 5-fluorouracil at 72 h was about 93.3% in PBS (pH 7.4) at 37 °C. Results of in vivo zebrafish toxicity tests and in vitro MTT assays of 1 at different concentrations reveal that 1 is nontoxic.

Structural diversity of a series of coordination polymers built from 5-substituted isophthalic acid with or without a methyl-functionalized N-donor ligand

The reaction of X-H2BDC (X = H, Br, NO2 and CH3) and methyl-functionalized dmbpy ligands with metal salts under different solvent media conditions generates nine structurally diverse zinc(II)/cadmium(II)-based coordination polymers (CPs), {[Zn2(BDC)2(DMF)3]·DMF}n (1), [Zn(BDC)2(dmbpy)]n (2), {[(Me2NH2)2Zn3(Br-BDC)4]·3DMF·3H2O}n (3), [Zn2(Br-BDC)2(dmbpy)]n (4), {[Zn13(NO2-BDC)8(μ3-OH)2(μ2-OH)6(H2O)4]·12H2O·2NO3}n (5), [Zn2(NO2-BDC)2(dmbpy)(H2O)2]n (6), {[Cd(NO2-BDC)(dmbpy)0.5(H2O)]·(ACN)·H2O}n (7), [Zn(CH3-BDC)(dmbpy)0.5(H2O)]n (8), and [Zn(CH3-BDC)(dmbpy)0.5]n (9) (H2BDC = isophthalic acid, Br-H2BDC = 5-bromoisophthalic acid, NO2-H2BDC = 5-nitroisophthalic acid, CH3-H2BDC = 5-methylisophthalic acid, dmbpy = 2,2′-dimethyl-4,4′-bipyridine, DMF = N,N-dimethylformamide, ACN = acetonitrile). All the compounds are synthesized using dual linkers (X-H2BDC and dmbpy). 1 and 7–8 show a 2D (4,4) network when dinuclear metal ions and ligands are regarded as nodes and linkers, respectively. 2 is a wave-like chain with BDC ligands alternately pointing up and down. CPs 3–6 and 9 all exhibit 3D networks with 5-connected sqp, 6-connected jsm, 6-connected pcu, (3,4)-connected dmc and 6-connected jsm topologies, respectively. Furthermore, luminescence, thermogravimetric and chemical stability properties of these CPs were investigated. The results suggest that both organic ligands and solvent media influence the final resulting CPs.

1-D Chain lanthanide coordination polymers based on mixed 2,4-dichlorophenoxyacetate and 1,10-phenanthroline ligands: crystal structures and luminescent properties

Two new isostructural 1-D lanthanide coordination polymers, {[Ln(2,4-dcp)3(phen)] n [(Ln = Eu (1); Tb (2)], [2,4-dcp = 2,4-dichlorophenoxyacetate, phen = 1,10-phenanthroline], were obtained under hydrothermal conditions and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. Both structures exhibit similar 1-D infinite chains with a {Ln2(2,4-dcp)6(phen)2} dimeric repeat unit, with lanthanides in an eight-coordinate environment. The results of thermal analysis indicate that 1 and 2 are quite stable to heat. 3-D fluorescence spectra of 1 and 2 were detected at room temperature under excitation and the emission wavelengths of 250–460 nm and 420–750 nm with the same interval of 5 nm, respectively. Interestingly, 1 and 2 possess longer fluorescence lifetimes than other complexes (τ = 1.61 ms for 1 at 611 nm; 1.79 ms for 2 at 543 nm).

Syntheses and structural characterizations of three transition metal coordination complexes based on flexible 2,4-dichlorophenoxyacetate (2,4-DCP)

Three transition metal coordination complexes, {[Co(2,4-DCP)2(μ 2-H2O)(H2O)2] · (H2O)2} n (1), [Zn(2,4-DCP)(IN)] n (2), and [Mn2(2,4-DCP)3(DMPY)2(μ 2-H2O)(H2O)] · (2,4-DCP) · 0.2(H2O) (3) (2,4-DCP = 2,4-dichlorophenoxyacetate, IN = isonicotinate, DMPY = 5,5′-dimethyl-2,2′-bipyridine), have been prepared under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a 1-D chain through cobalt and bridging water molecules with Co ··· Co distance of 4.028(2) Å. Complex 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak hydrogen-bonding interactions. Complex 3 consists of discrete dinuclear cations, 2,4-DCP counter ions and free water molecules, which are assembled into a packing structure through π ··· π stacking of inversion-related DMPY ligands and hydrogen bonds. Magnetic susceptibility measurements show weak antiferromagnetic interactions in 1. The photoluminescence and lifetime of 2 in the solid state have also been studied.

Solvent-dependent structural diversity of cadmium(II) coordination polymers: syntheses, characterizations, and luminescence properties

Abstract By changing the solvent, three cadmium(II) coordination polymers (CPs), [Cd(NH2-BDC)(DMA)(H2O)]n (1), {[Cd(NH2-BDC)2(DMF)2]·H2O}n (2) and {[(Me2NH2)2Cd2(NH2-BDC)3(H2O)]·DMF·8H2O}n (3), have been synthesized based on the V-shaped linker 5-aminoisophthalic acid and Cd(NO3)2·4H2O under the same reaction temperature (140 °C) (NH2-BDC = 5-aminoisophthalate, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide). Compound 1 features a 1-D ladder-like infinite chain. Compound 2 is a 2-D (4,4) net when the dinuclear [Cd2(COO)4O4] is regarded as a quadruply-connected node. Compound 3 shows a 2-D hamburger-like structure. Luminescent properties of 1–3 were detected at room temperature under the same excitation and emission wavelengths of 200–600 nm with the same interval of 5 nm. Moreover, the calculation of lattice constants and volumes, and density of states of CPs 1 and 2 were carried out to get better insight into the nature of the structure and luminescence.

Construction of two lanthanide complexes based on N- and O-donors: synthesis, luminescence, and biological activities

Two new isostructural dinuclear complexes, Ln2(4-cpa)6(phen)2 (Ln = Eu (1); Tb (2), 4-cpa– = 4-chlorophenylacetate, phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The lanthanides are bridged by two bidentate and two tridentate carboxylato groups to give centrosymmetric dimers with Ln···Ln separations of 3.967(2) and 3.937(3) Å for 1 and 2, respectively. Each metal is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Both 1 and 2 emit characteristic, intense luminescence at room temperature with lifetimes up to 0.890 ms (at 611 nm) and 0.995 ms (at 543 nm). Poor luminescence efficiency is observed for 2. 4-Chlorophenylacetate, 1 and 2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl. Graphical Abstract

Hydrothermal synthesis, crystal structure, and photoluminescence of a new 2D cadmium(II) complex: {Cd(C8H5O3Cl2)2(C10H8N2)}n

One new cadmium coordination polymer, [Cd(2,4-Dcp)2(4,4-Bipy)]n (I) (2,4-HDcp = 2,4-dichlorophenoxyacetic acid, 4,4′-Bipy = 4,4′-bipyridine) with 2D layer structure, has been prepared by the hydrothermal synthesis and characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. Complex I crystallizes belong to monoclinic system and has C2/c space group. Each Cd2+ ion is six-coordinated and located at an octahedral geometry. The Cd2+ ions are linked by bidentate 2,4-Dcp groups into a linear chain in which the benzene rings of 2,4-Dcp ligands point alternately up and down. These chains are further connected into a sandwich-like layer though 4,4′-Bipy ligands. Furthermore, the photoluminescence and life-time of I in the solid state have been studied.

CCDC 1566031: Experimental Crystal Structure Determination

Related Article: De-Yun Ma, Jiamin Xie, Zhiwei Zhu, Hailan Huang, Yutao Chen, Rongxing Su, Huimin Zhu|2017|Inorg.Chem.Commun.|86|128|doi:10.1016/j.inoche.2017.10.007

Structure and characterization of A 2D cobalt(II) complex [Co(L)2] n (L = 3-nitro-5-(pyridine-4-yl)benzoate)

The self-assembly of unsymmetrical tecton 3-nitro-5-(pyridin-4-yl)benzoic acid (HL)with cobalt chloride under hydrothermal conditions affords a new 2D coordination polymer [Co(L)2]n (1, L = 3-nitro-5-(pyridin-4-yl)benzoate), which is characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction analysis, and single crystal X-ray diffraction. Compound 1 is of the triclinic system, space group P-1 with a = 9.7857(12) Å, b = 10.3417(13) Å, c = 10.8463(13) Å, α = 85.155(2)°, β = 74.785(2)°, γ = 88.962(2)°, V = 1055.4(2) Å3. The crystal structural analysis of complex 1 shows that the cobalt center is six-coordinated in an octahedral geometry by four O atoms from four different L ligands and two N atoms from two different L ligands; the Co(II) cations are bridged by μ3-L into an interesting two-dimensional network structure. It should be pointed out that the thermal analysis results indicate that complex 1 is quite stable up to 420°C.