Isolation of a metastable intermediate in a heterometallic Cu(II)-Hg(II) 1D polymeric chain: synthesis, crystal structure, and photophysical properties.

A metastable heterometallic intermediate, [Cu2(bpy)2(DIPSA)2Hg2(OAc)4(DIPSA)2]n (1, where OAc = CH3COO(-), bpy = bipyridine, and DIPSA = diisopropylsalicylic acid), has been isolated and characterized during the synthesis of 1D polymer [Cu2(bpy)2(DIPSA)2(CH3CN)2Hg2(OAc)2(DIPSA)4]n (2) at ambient temperature in acetonitrile. Moreover, recrystallization of 2 in methanol results in monomeric [Cu(DIPSA)(bpy)(CH3OH)]·CH3OH (3). Complexes 1-3 have been characterized by elemental analysis, Fourier transform infrared, and UV-vis spectroscopy as well as by their single-crystal X-ray structures. The photophysical study suggests the quenching of fluorescence of DIPSA upon complexation.

Bis[2-(2-hy-droxy-meth-yl)pyridine-κ(2)N,O](pivalato-κO)copper(II).

The structure of the centrosymmetric title complex, [Cu(C(5)H(9)O(2))(2)(C(6)H(7)NO)(2)], has the Cu(II) atom on a centre of inversion. The Cu(II) atom is six-coordinate with a distorted octa-hedral geometry, defined by the N and O atoms of the chelating 2-(2-hydroxymethyl)pyridine ligands and two carboxyl-ate O atoms from two monodentate pivalate ions. The crystal packing is stabilized by inter-molecular C-H⋯O and intra-molecular O-H⋯O hydrogen-bond inter-actions.

A highly selective, sensitive and reversible fluorescence chemosensor for Zn(2+) and its cell viability.

A new imine conjugate Schiff base ligand (H2L) was prepared and evaluated for its sensing properties. H2L detects Zn2+ selectively among the wide range of metal ions. The sensing behavior of H2L was identified by UV-vis, fluorescence and 1H NMR titration. H2L shows fluorescence switch ON with the Zn2+ ion among 18 other metal/heavy metal ions with a detection limit of 1.47 µM. The binding of Zn2+ was confirmed by single crystal X-ray studies, which reveal the formation of binuclear complex (1). The packing diagram of H2L reveals the presence of rare linear C­H⋯C interactions (bond distance 2.79 Å and bond angle 180°) which form 1D-polymeric chains. Furthermore, the cytotoxicity of H2L and 1 has been assessed against MCF-7 and A375 cell lines and both are found to have marginal toxicity.

Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties.

Reactions of the amide ligand, H2L (H2L = N,N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide) with CdCl2 and Hg(CH3COO)2, in 1 : 1 ratio, at 298 K yield dimeric [Hg(L)]2 (1) and trimeric [Cd3(H2L)4Cl6] (2), respectively. In 1, the H2L is coordinated to Hg(II) via six N-atoms of central and terminal pyridines as well as of deprotonated amido groups, whereas the carbonyl groups remain free. However, in 2, the H2L is coordinated to Cd(II) through terminal pyridine N atoms and O atoms from carbonyl groups, whereas the nitrogen atoms of the central pyridine, two terminal pyridine and of all amido groups remain free. Molecular structures of 1 and 2 are confirmed by single crystal X-ray studies. The varying coordination modes of H2L give rise to different electrochemical behavior of 1 and 2, which has also been rationalized by theoretical calculations. Moreover, nonlinear optical (NLO) behavior of both complexes has been investigated using ultra-short femtosecond laser pulses, which ensures that the NLO response is exclusively from their electronic component.

Swift photoswitching in a binuclear Zn(II) metallacycle relative to a salen-type ligand.

The synthesis, characterization and photoswitching behavior of a new salen type Schiff base N,N'-bis(2-hydroxy-5-phenylazobenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H2L) and a binuclear zinc(ii) metallacycle [{Zn(L)}2·2H2O] (1) have been described. Both H2L and 1 have been characterized by satisfactory elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission) and electrochemical studies. Crystal structures of both H2L and 1 have been authenticated by single crystal X-ray diffraction analyses. These exhibit trans-cis photoisomerization upon exposure to UV light (365 nm) and get back to a more stable trans-form after withdrawal of the light. Electronic absorption, emission, (1)H NMR and cyclic voltammetric studies revealed that trans-cis isomerization in metallacycle 1 is rather rapid (~5.0 s) relative to H2L (~25 s) which has been supported by theoretical studies (DFT). Relatively fast photoisomerization in 1 compared to H2L is facilitated by a small energy gap between HOMO levels of the trans- and cis-isomers. The percentage trans-cis conversion ratio for both H2L and 1 has been evaluated (55-45, H2L; 60-40%, 1) by (1)H NMR studies.

Formation of a 1D-polymeric chain of Hg building blocks through C-C coupling under ambient conditions.

A novel C-C coupled 1D-polymeric chain (1) is obtained by reaction of HgCl2 and hmp-H (2-(2-hydroxymethyl pyridine)) (1 : 1) in MeOH at ambient temperature. However, a new class of µ-oxo and µ-chloro bridged polymers (2) has been obtained by altering the metal : ligand ratio to 1 : 2.