A series of ZnII and CdII complexes with a flexible dicarboxylate building block and various heterocyclic co-ligands, formulated as {[Zn2(pda)2(phen)2]·2H2O}n (1), {[Zn(pda)(dpe)]·H2O}n (2), [Zn(pda)(bpp)]n (3), {[Cd2(pda)2(2,2′-bipy)2]·2H2O}n (4), {[Cd(pda)(4,4′-bipy)(H2O)]·H2O}n (5) and {[Cd2(pda)2(bpp)3]·14H2O}n (6) (pda = 1,3-phenylenediacetate, phen = 1,10-phenanthroline, dpe = 1,2-di(4-pyridyl)ethylene, bpp = 1,3-bi(4-pyridyl)propane, 2,2′-bipy = 2,2′-bipyridine, and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and structurally characterized. In 1, the (H2O)8clusters interlink the cyclic coordination dimers to give a 3D network through hydrogen bonding. Both 2 and 3 feature 2D corrugated (4,4) layers, which are of 2-fold interpenetrating for 3. In 4, the dimeric CdII subunits are connected by the 1,3-pda ligands to generate a rampart-shaped 1D chain motif. As for 5, the [Cd(pda)]2 rings are connected by the paired 4,4′-bipy ligands to afford a tube-shaped 1D motif. In contrast to 1–5, complex 6 displays a 3D diamond network and, interestingly, the T5(0)A(0)A(2) water tapes are found to locate in the channels of this 3-D array. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands (from chelating to bridging) play a key role in governing the coordination motifs as well as the 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stability of 1–6 have also been studied.

Structural diversity and properties of ZnII and CdII complexes with a flexible dicarboxylate building block 1,3-phenylenediacetate and various heterocyclic co-ligands

Three new silver(I) metal−organic frameworks (MOFs), namely, [Ag2(pda)(bipy)2]n·4nH2O (1), [Ag2(pda)(dpe)2(H2O)]n·4nH2O (2), and [Ag(Hpda)(bpp)]n (3), were prepared by hydrothermal reactions of silver(I) acetate with H2pda (H2pda = 1,2-phenylenediacetic acid) in the presence of different pyridyl-containing ligands (bipy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)-ethylene, and bpp = 1,2-bis(4-pyridyl)propane) and structurally characterized by single crystal X-ray diffraction Complex 1 shows a two-dimensional (2D) four-connected network with a long topological vertex Schlafli symbol (462463646) Of particular interest, a new unreported octameric water cluster, (H2O)8, which is comprised of a cyclic water tetramer and four dangling water monomers, exists in 1 And the pseudorotaxane motifs are formed by these octameric clusters and the [Ag8(pda)2(bipy)4] loops Complex 2 features a one-dimensional (1D) ladder-like chain structure, and the 2D networks, assembling by the combination of the pentameric wat

Formation of Three New Silver(I) Coordination Polymers Involving 1,2-Phenylenediacetic Acid via the Modulation of Dipyridyl-Containing Ligands

Four novel Zn(II) and Cd(II) coordination polymers, {[Zn(cmb)(dpa)]·H2O}n (1), {[Zn(cmb)(bpp)]·2.5H2O}n (2), {[Zn(cmb)(bimb)]·3H2O}n (3), and {[Cd2(cmb)2(bimb)]·H2O}n (4) (H2cmb = 2-(carboxymethoxy)benzoic acid; dpa = 4,4′-dipyridylamine; bpp = 1,3-di(4-bipy)propane; bimb = 1,4-bis(imidazol)butane), have been synthesized and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1 exhibits a diamond (dia) framework of four-fold interpenetration (class IIIa). 2 features a rare 1D → 3D polycatenated architecture, which is built from the interlocking of two sets of 1D supramolecular loops running in different directions (almost perpendicular). The 3D crystalline lattice of 3 is constructed through the parallel packing of corrugated 2D 44 (sql) nets. Complex 4 shows a 2D network with the (3,4)-connected (43)2(4 × 104 × 12)(42 × 104) topology, which consists of 1D [Cd(cmb)]n arrays and helical pillars. The results clearly indicate the importance of linking modes of organic ligands and metal centers as well as the auxiliary ligands in the direction of the diverse structures for complexes 1–4. Thermal stabilities and luminescent properties of complexes 1–4 have also been investigated.

Structural diversity and fluorescent properties of Zn(II)/Cd(II) coordination polymers with a versatile tecton 2-(carboxymethoxy)benzoic acid and N-donor co-ligands

Eight imidazole-based compounds 4-methyl-2,6-bis(4,5-diphenyl-1H-imidazol-2-yl)phenol ( A-dp), 2-(1H-phenanthro[9,10-d]imidazol-2-yl)phenol ( B-2H), 5-methoxy-2-(1H-phenanthro[9,10-d]imidazol-2-yl)phenol ( B-2H4M), 3-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol ( C-3H), 2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-4-methoxyphenol ( C-2H5M), 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol ( C-4H3M), 2-(2-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ( C-2M) and 2-(2,4-dimethoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ( C-2,4M) were synthesized and characterized by elemental, spectroscopic and X-ray single crystal analyses. Two different crystals of A-dp were grown from ethanol and THF, which revealed that A-dp crystallizes in a monoclinic (P2(1)/c) space group while A-dp·2THF crystallizes in a triclinic (P) space group. A-dp·2THF was devoid of any kind of networks whereas the absence of solvent adducts in the ethanol sample produces 1-dimensional single-stranded helices. Contrary to the reported literature conclusion that 1H-imidazole alkylation should increase the donor strength of the imidazole N-base, protonation–deprotonation equilibrium studies on the compounds suggest that push/pull of electron density on the 2-carbon of the imidazole ring by electron-rich/electron-withdrawing substituents is necessary to influence donor capacity of the N-base electrons. Furthermore, the notable increase in pKa,N: values due to ortho/para-directing methoxy substituents supports the conclusion that electron density push towards the 2-position of the imidazole ring is important for improving N-base donor strengths. DFT calculation results using the B3LYP/6-311+G level of theory were conducted to explore possible theoretical explanations.

Electronic/substituents influence on imidazole ring donor–acceptor capacities using 1H-imidazo[4,5-f][1,10]phenanthroline frameworks

Luminescent properties of some imidazole and oxazole based heterocycles: Synthesis, structure and substituent effects

A zinc(II) coordination polymer, [Zn4(o-bda)4(p-pbim)4] n (1) (p-pbim = 4-pyridylbenzimidazole, o-bda2− = o-phenylenediacetic acid dianion), has been synthesized by hydrothermal method and characterized by elemental analysis, IR, TG, photoluminescence and X-ray single crystal diffraction. Complex 1 crystallizes in a monoclinic system and space group P21 /n, with a = 14.231(3) A, b = 16.257(4) A, c = 16.794(4) A, β = 100.262(1)°, and Z = 8; R 1 for 6475 observed reflections [I > 2σ(I)] was 0.0420. Complex 1 shows a bi-chain structure fabricated by the tetranuclear zinc unit. Two zinc(II) ions are five coordinate with distorted trigonal-bipyramid geometry; the other two zinc(II) ions are four coordinate with distorted tetrahedral geometry. Complex 1 builds the 1-D bi-chain structure with two different subrings A and B, which are 32-member and 14-member rings, respectively. There exists a 2-D supramolecular network linked by hydrogen-bonding interactions (2.695 and 2.807 A). A 3-D supramolecular network is f...

A zinc(II) coordination polymer, [Zn4( o -bda)4( p -pbim)4] n , with strong blue fluorescence

Supramolecular networks of hexanuclear cadmium (II): Synthesis, crystal structure and emission property

In the title compound, [Cd2(C10H8O4)2(C12H8N2)3(H2O)]·0.79C2H6O·3.05H2O, the two independent CdII atoms in the asymmetric unit have different coordination modes. One is six-coordinate and the other is seven-coordinate, forming distorted octa­hedral and monocapped octa­hedral geometries, respectively. The CdII atoms are bridged by o-phenyl­enediacetate ligands to form a one-dimensional chain structure, which is further linked into a two-dimensional network through O—H⋯O hydrogen bonds.

catena‐Poly[[[aqua(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κ2O,O′:κO′′‐[bis(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κO:κ2O′,O′′] ethanol 0.79‐solvate 3.05‐hydrate]

The —OCH2CO2 arm of the ligand in the title compound, [Zn(C9H6O5)(H2O)]n, uses the single-bond carboxyl O atom, as well as the ether O atom, to chelate to the Zn atom; the other —CO2 arm bridges adjacent Zn atoms into a helical chain that propagates by means of a 21 screw axis. The —OCH2CO2 arm features distinct single- and double-bond C—O distances; in the other —CO2 arm, the C—O distances are interpreted in terms of a delocalized carboxyl group. The coordination about zinc is completed by a water mol­ecule, resulting a distorted ZnO5 square-pyramidal arrangement in which the apical position is occupied by water.

catena-Poly[[aquazinc(II)]-μ-2-carboxylatophenoxyacetato]

In the title compound, [Zn(C5H5N2O2S)2(H2O)], the central Zn atom (2 site symmetry) is five-coordinated by two N and three O atoms [Zn—N = 2.047 (3) A, Zn—O = 2.099 (2) and 1.974 (4) A] in a distorted square-pyramidal geometry. Besides one O atom from a water mol­ecule, two 2-amino­thia­zole-4-acetate ligands provide two N and two O atoms as coordinated atoms. In the crystal structure, inter­molecular O—H⋯O and N—H⋯O hydrogen bonds connect the mol­ecules into an infinite three-dimensional framework.

https://journals.iucr.org/e/issues/2009/12/00/rk2177/rk2177.pdf

Yan Yang

Papers

A zinc(II) coordination polymer, [Zn4( o -bda)4( p -pbim)4] n , with strong blue fluorescence

Supramolecular networks of hexanuclear cadmium (II): Synthesis, crystal structure and emission property

catena‐Poly[[[aqua(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κ2O,O′:κO′′‐[bis(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κO:κ2O′,O′′] ethanol 0.79‐solvate 3.05‐hydrate]

catena-Poly[[aquazinc(II)]-μ-2-carboxylatophenoxyacetato]

Bis(2-aminothiazole-4-acetato)aquazinc(II)

Yan Yang

Papers

A zinc(II) coordination polymer, [Zn4( o -bda)4( p -pbim)4] n , with strong blue fluorescence

Supramolecular networks of hexanuclear cadmium (II): Synthesis, crystal structure and emission property

catena‐Poly[[[aqua(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κ2O,O′:κO′′‐[bis(1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ‐o‐phenylenediacetato‐κO:κ2O′,O′′] ethanol 0.79‐solvate 3.05‐hydrate]

catena-Poly[[aquazinc(II)]-μ-2-carboxylatophenoxyacetato]

Bis(2-amino­thia­zole-4-acetato)aquazinc(II)

Bis(2-aminothiazole-4-acetato)aquazinc(II)