A novel Cu(II)-MOF {[Cu-4(TTTMB)(4)(NO3)(4)(H2O)5]center dot(NO3)2 center dot(I-3)(2)center dot H2O}(n) containing polyiodide I-3(-) was obtained through crystal to crystal transformation by immersing a Cd II complex {[Cd-3(TTTMB)(4)I-2]center dot I-4}(n) in an aqueous solution of Cu(NO3)(2). There are two kinds of I-3(-) arranged as infinite zigzag center dot center dot center dot I-3(-)center dot center dot center dot I-3(-) chains between the layers of the Cu(II)-MOF.

To investigate the influence of spatial extended direction and flexibility of secondary ligand on the resulting structure, eight new ferrocene-containing complexes with various dimensionalities have been synthesized by the reactions of Cd-II salts and 1,1'-bis(3-carboxy-1-oxopropyl)ferrocene (H(2)bfcs) with series of rationally selected N-heterocyclic spacers. When the small organic molecule 4-aminopyridine (apy) was employed as a secondary ligand, a one-dimensional (1D) linear complex {[Cd(bfcs)(apy)(2)] center dot H2O}(n) (1) was furnished, while the use of bis(azole) bridging ligands resulted in the formation of a 1D ribbon complex {[Cd(bfcs)(bbbm)(1.5)] center dot CH3OH center dot 2H(2)O}(n) (2), a rare 1D quadruple-chain complex {[Cd(bfcs)(btmb)] center dot 3H(2)O)(n) (3) and two two-dimensional (2D) puckered complexes {[Cd-2(bfcs)(2)(pbbm)(2)]center dot 2H(2)O}(n) (4) and {[Cd(bfcs)(bix)]center dot H2O}(n) (5) (bbbm = 1,1'-(1,4- butanediyl)bis-1H-benzimidazole, btmb = 4,4'-bis(1,2,4-triazole-1-ylmethyl)biphenyl, pbbm = 1,1'-(1,3-propanediyl)bis-1H-benzimidazole, bix = 1,4-bis(imidazole-1 -ylmethyl)benzene). In addition, the tripodal bridging secondary ligand led to an unusual three-dimensional (3D) layer pillar complex {[Cd-2(bfcs)(titb)(2)Cl-2]center dot 2CH(3)OH center dot 4H(2)O}(n) (6) (titb = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene). Employment of a flexible multidentate molecule tris(2-benzimidazolylmethyl)amine (ntb) as the secondary ligand gave birth to a mononuclear complex [Cd(bfcs)(ntb)]center dot DMF center dot 5H(2)O (7) and a binuclear complex [Cd-2-(bfcs)(ntb)(2)]center dot bfcs center dot 5H(2)O (8), in which ntb adopted the chelating coordination mode. It can be observed from the coordination architectures of 1-8 that secondary ligands had great effects on the spatial connective fashions of Cd-II centers, resulting in the formation of various dimensional complexes.

Using ferrocenyl carboxylates as functional ligands, we synthesized a mononuclear complex [Zn(eta(2)-OOCCH= CHFc)(2)(CH3OH)(2)] (1) and a binuclear complex [Cd(bafca)(2)(H2O)(2)](2) (2) (bafca = alpha-benzamido-beta-ferrocenylacrylic carboxylate) as precursor complexes. Investigation on the substitution reaction of precursor complexes as building blocks in solution-state, four complexes [Zn(OOCCH=CHFc)(2)(bbbm)](n) (1a), {[Zn(OOCCH=CHFc)(ntb)](CH3OH)} (1b), [Cd(bafca)(2)(2,2'-bpy)](2) center dot 9H(2)O (2a) and {[Cd(bafca) (2)(bbbm)(CH3OH)(2)] center dot 6CH(3)OH}(n) (2b) were obtained (bbbm = 1,1-(1,4-Butanediyl) bis-1H-benzimidazole, ntb = N, N-bis(1H-benzimidazol-2-ylmethyl)-1H-Benzimidazole-2-methanamine and 2,2'-bpy = 2,2'-bipyridine). As anticipated, the structural integrity of precursor complexes can be maintained in these four complexes. It indicates that we can synthesize the desired complexes with the destination structures by using precursor complexes as building blocks and choosing appropriate auxiliary ligands. In addition, the electrochemical properties of all complexes were investigated, and it can be seen from the results that half-wave potentials of these complexes are slightly higher than that of the corresponding ligand. (C) 2008 Published by Elsevier B.V.

Reaction of a rigid conjugated clamp-like multi-pyridine ligand N,N'-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide (H2L) with CuSO4 center dot 5H(2)O or Cu(OAc)(2) resulted in the formation of two high-nuclearity, discrete molecular copper(II) complexes, namely [Cu-10(H2L)(5)(SO4)(8)(mu(3)-OH)(4)(H2O)(2)]center dot 4CH(3)-CH2OH center dot 7H(2)O (1) and [Cu-6(L)(4)(CH3COO)(4)]center dot 2DMF center dot 6H(2)O (2). In 1, ten copper atoms are engaged by five H2L ligands, eight SO42- and four mu(3)-OH groups to form a novel decanuclear copper complex which sits on a crystallographic twofold axis passing through the centre of the complex. The structure of 2 features a hexanuclear copper cage and a crystallographic centre of inversion is at the mid-point of the compound. The rigid conjugated clamp-like H2L ligands, polydentate in nature, form a "coordination pocket" arising from their "arms" to entrap the copper atoms and play an important role in the assembly of discrete molecular high-nuclearity complexes 1 and 2. Applications of 1 and 2 as heterogeneous catalysts for the oxidative polymerisation of 2,6-dimethylphenol showed very promising results at ambient temperature and these novel catalytic systems are very mild, efficient, regioselective and easily recyclable. The interesting catalytic properties of 1 and 2 can be attributed to their particular structural characteristics and their unusual reactivities based on cooperativity or electron transfer between multicopper centres. Magnetic studies of these copper(II) cages indicate antiferromagnetic behaviour. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Three new polymers, namely, {[Cd(TTTMB)(bdic2−)(H2O)]·H2O}n (1), {[Cd(TTTMB)(Hbtrc2−)(H2O)]·2H2O}n (2) and [Zn(TTTMB)(Hbtrc2−)(H2O)]n (3) based on a flexible tripodal ligand 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (TTTMB) have been synthesized by choosing H2bdic and H3btrc as auxiliary ligands under hydrothermal reaction (H2bdic=1,3-benzenedicarboxylic acid and H3btrc=1,3,5-benzenetricarboxylic acid). The structures of the polymers were determined by single-crystal X-ray diffraction analyses, and the results reveal that 1 and 2 exhibits a two-dimensional (4,4) network. While the crystal structure of 3 shows one-dimensional zigzag chain. Additionally, the solid-state fluorescent properties of these three polymers and ligand TTTMB were investigated at room temperature.

With the use of sodium beta-ferrocenylacrylate and sodium p-ferrocenylbenzoate as functional ligands, we synthesized mononuclear precursor complexes containing facile leaving groups or coordinatively unsaturated metal ions: [Cd(eta(2)-OOCCH=CHFc)(2)(C2H5OH)(2)] (1), {[Cd(eta 2- -OOCC(6)H(4)Fc)(2)-(dmf)(2)(H2O)]} (2), {[Cd(eta(2)-OOCC(6)H(4)Fc)(2) (phen)(H2O)]-(CH3OH)) (3), and {[Zn(OOCC(6)H(4)Fc)(2)(phen)](H2O)} (4) (phen = 1,10-phenanthroline). Investigation of the four precursor ferrocenyl carboxylate complexes as building blocks resulted in ten complexes. The complexes {[Cd(eta(2)-OOCCH=CHFc)(2)(bbbm)](H2O)}(n) (1a), {[Cd-2(eta(2)- OOCCH=CHFc)(4) (pbbm)(2)](CH3OH)(6)(H2O)(4)} (1b), {[Cd(eta(2)- OOCC(6)H(4)Fc)(2)(py)(3)] (CH3OH)(4)} (2a), {[Cd-2(eta(2)- OOCC(6)H(4)Fc)(2)(phen)(2)(bbbm)] (CH3OH)(2)} (2b), {[Cd-2(eta- OOCC(6)H(4)Fc)(2)(OOCC(6)H(4)Fc)(2)(phen)(2)(bbbm)] (CH3OH)(4)(thf)(2)} (3a), and [Zn(OOCC(6)H(4)Fc)(2)(phen)(H2O)] (4a) were obtained by the substitution or addition reactions of the precursor complexes under moderate conditions. As anticipated, the structural integrity of the precursor complexes can be maintained from the precursors to these complexes. We designed the structures of the complexes by controlling the number of leaving groups in the precursor complexes. In addition, a recombination may have taken place in the reactions of the precursor complexes with organic ligands under severe conditions. The "recombinant" complexes {[Cd-2(eta(2)-OOCCH=CHFc)(2)(mu(2)-eta(2)-OOCCH=CHFc)(2)(L)(2)](CH3OH)(4)}(n) [L = 1,4-bis(imidazol-1-yl-methyl)benzene (bix), 1c; L = btx, 1d], {[Cd(eta(2)-OOCC(6)H(4)Fc)(2)(pbbm)(H2O)](H2O)}(n) (3b) and ([Zn(OOCC(6)H(4)Fc)(2)- (bbbm)](CH3OH)(3)}(n), (4b) were also obtained under reflux conditions. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).