Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes (original) (raw)
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Polyhedron, 2013
Four new coordination polymers namely, [Cd 3 (L 1) 2 (DMA) 4 ] n (1), [Mn(HL 1)(H 2 O) 3 ] n (2), [Mn(H 2 L 2)] n (3) and {[Co 2 (HL 2)(L 2)]Á(Et 4 N)Á(1.5H 2 O)} n (4) have been synthesized with semi-rigid ether bridged tricarboxylic acid ligands H 3 L 1 and H 3 L 2 [H 3 L 1 = 5-(4-carboxy-phenoxy)-isophthalic acid and H 3 L 2 = 5-(2-carboxyphenoxy)-isophthalic acid] with various transition metal ions using hydro(solvo)thermal techniques. All the coordination polymers have been structurally characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and X-ray single crystallography. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric to trimeric units except 2 which is a linear monomeric. On reacting para-isomer of the ligand H 3 L 1 with metal ions, 2D and 3D supramolecular structures have been obtained while with the ortho-isomer H 3 L 2 dimeric 2D and 3D framework were obtained. Topological analysis reveals that 1 and 3 are binodal (3,6)-connected kgd net, 2 is also a binodal (3,3)-connected honeycomb type hcb net, while 4 shows unprecedented (3,3,6)-connected pkb5 topological trinodal-network. Interestingly, 3 and 4 exhibits unusual coordination modes involving one of carbonyl O atom of an acid functional group. Moreover, in 4 ethereal O atom is also coordinated to one of the metal center. All complexes show high thermal stability, thus losing coordinated and lattice solvent molecules in the range, $100-200°C. Upon excitation at 325 nm, compounds 1-4 exhibit solid-state luminescences at room temperature.
European Journal of Inorganic Chemistry, 2011
The organodiselone ligands 1,1-bis(3-methyl-4-imidazolin-2selone)methane (L1) and 1,2-bis(3-methyl-4-imidazolin-2-selone)ethane L2) have been used for the synthesis of homopolynuclear Tl I [{Tl(L)}PF 6 ] n ·(mMeCN) n [L = L1, m = 1 (1); L = L2, m = 0 (2)] and discrete heteropolynuclear [Tl{Au-(C 6 Cl 5 ) 2 }(L)] [L = L1 (3), L2 (4)] complexes. The crystal structures of complexes 1 and 3 have been determined through X-ray diffraction studies. Complex 1 consists of alternating thallium(I) centres and bidentate Se-donor ligands that result in polymeric chains. The crystal structure of 3 is formed by [Tl(L1)] + cations and [Au(C 6 Cl 5 ) 2 ]anions joined together by an unsupported Au···Tl interaction. Compounds 3 and 4 are
Inorganica Chimica Acta, 2020
Five new Tl(I) coordination compounds based on aryl monocyanoximes, such as phenylcyanoxime-HPhCO, 1, 2fluorophenylcyanoxime-H(2F-PhCO, 2, 3-fluorophenylcyanoxime-H(3F-PhCO), 3, of TlL composition, and aryl biscyanoximes, such as 1,3-cyanoxime (benzene)-H 2 (1,3-BCO, 4 and 1,4-cyanoxime (benzene)-H 2 (1,4-BCO), 5 of Tl 2 L stoichiometry were synthesized and characterized using spectroscopic methods, thermal stability studies, and X-ray analysis. All obtained complexes represent coordination polymers of different complexity, ranging in dimensionality from 1D in Tl(2F-PhCO) to 3D in Tl 2 (1,3-BCO). The most interesting feature of all synthesized complexes is the formation of Tl 2 O 2 rhombs: non planar and non-centrosymmetric in Tl(PhCO), and planar and centrosymmetric in the other three compounds. These rhombi are interconnected, forming zigzag and ladder-type polymers in which very short thallophilic Tl-Tl distances were observed. Thus, in the structure of Tl 2 (1,3-BCO) the closest distance between metal centers was found to be 3.670 Å. This is the second shortest onrecord intermetallic contact in non-organometallic and non-cluster, but Werner type complexes, and is close to that in metallic thallium: 3.456 Å. In all five new coordination polymers the central atom has a stereo-active 6 s 2 lone pair that significantly distorts the shape of the coordination polyhedron of Tl(I). The first time, Tl-O vibrations in Tl 2 O 2 rhombs were observed in Raman spectra of the obtained complexes. Thermal analysis studies evidenced stability of all complexes, but Tl(PhCO), to ∼200°C. The Tl 2 (1,3-BCO) compound demonstrates properties of the high energy compound, and violently exothermically decomposes at ∼255°C with the release of a significant amount of kinetic energy. The final product of anaerobic decomposition of all studied Tl-cyanoximates is metallic thallium sponge.
Chemical Communications, 2012
Elemental analyses were carried out with a Perkin-Elmer 2400 CHNS/O microanalyzer. IR spectra were recorded on a Nicolet Nexus FT-IR Spectrometer from Nujol mulls between polyethylene sheets. Complex 1 is the only soluble enough to register its 1 H and 13 C NMR spectra, being recorded on a Bruker ARX 300 spectrometer; chemical shifts are reported in ppm relative to external standars (TMS and CFCl 3 respectively) and coupling constants in Hz. MALDI-TOF spectra was recorded on a Microflex MALDI-TOF Bruker spectrometer operating in the linear and reflector modes using dithranol (DIT) as matrix. The Molar Conductivity of complex 1 was measured in acetone solution (5 × 10-4 M) using a Crison GLP31 conductimeter. UV-Vis spectrum of complex 1 was recorded on a Hewlet Packard 8453 spectrometer. Excitation and emission spectra were obtained on a Jobin-Yvon Horiba Fluorolog 3-11 Tau-3 spectrofluorimeter. The lifetime measurements were performed operating in the phosphorimeter mode (with a F1-1029 lifetime emission PMT assembly, using a 450 W Xe lamp). [trans-Pt(C≡CTol) 2 (PPh 3) 2 ] 1 and K(HBpz 3) 2 were prepared as reported and other reagents were obtained from commercial sources. Computational details for DFT calculations. All DFT calculations were carried out using the Gaussian 03 3 package applying the Becke's 3-parameter hybrid function combined with the Lee-Yang-Parr correlation function (B3LYP). 4 The basis set used was the LanL2DZ effective core potential 5 for the metal centers (Pt, Tl and Pb) and 6-31G(d,p) for the ligand atoms. The anion [trans-Pt(C≡CTol) 2 (CN) 2 ] 2of complex 1 was optimized under vacuum by isolating it from the X-ray structure of 2. No negative values were found in the results of the vibrational frequency analysis. Single point
Polyhedron, 2013
When the ligand HH 0 L was treated with different transition metal salts at room temperature, four new isostructural coordination polymers, {[Zn(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (1), {[Cd(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (2), {[Mn(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (3), and {[Co(H 0 L) 2 (H 2 O) 2 ]Á2DMF} n (4) (HH 0 L = 2-hydroxy-5-(pyridin-4ylazo)-benzoic acid) were formed. These polymers were characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), in addition to X-ray crystallography. X-ray single crystal studies revealed that 1-4 are 1D coordination polymers that are further extended by weak interactions to afford 3D coordination polymers. All the complexes show high thermal stability after losing coordinated and lattice solvent molecules in the temperature range 80-200°C. Upon excitation at 344 nm, complexes 1-4 exhibit solid-state luminescence at room temperature.
Polyhedron, 2019
A mixed ligand approach has been applied for the synthesis of a series of Zn(II) and Cd(II) coordination polymers, namely CP1 [{Zn(3-bpna)(bdc)}•CH3OH]α, CP2 [{Cd(3-bpna)(oba)}•DMF•H2O]α, CP3 [{Cd(3-bpna)(5-nipa)}•2DMF]α, CP4 [{Zn2(dpmndi)(oba)3}•4H2O]α, CP5 [{Zn(dpmndi)0.5(oba)•DMF}•DMF•H2O]α and CP6 [{Cd(dpmndi)(bdc)}•DMF]α, which are constructed by the reactions of the ligand 3-bpna or dpmndi and Zn(NO3)2•6H2O or Cd(NO3)2•4H2O in the presence of different dicarboxylate ligands, specifically terephthalic acid, 4,4'-oxydibenzoic acid and 5-nitroisophthalic acid, as a co-ligand under solvothermal conditions. These coordination polymers were structurally characterized and display 1D, 2D and 3D network structures. Moreover, their fluorescent behavior was also investigated and the results are found to be very promising.