Solvothermal reactions of bulk CuSCN with six flexible benzimidazolyl-based ligands with different spacer lengths [(bzim)(CH 2 ) n (bzim)] (bzim = benzimidazolyl; n = 1, mbbm; n = 2, ebbm; n = 3, prbbm; n = 4, bbbm; n = 5, pbbm; n = 6, hbbm) afforded a series of new [CuSCN] n -supported coordination polymers, [(CuSCN) 2 5), and [(CuSCN) 2 (hbbm)] n (6), respectively. Compounds 1-6 were characterized by elemental analysis, IR, and X-ray crystallography. Compound 1, 3a, or 6 possesses the similar staircase-like [CuSCN] n chains that are bridged by mbbm, prbbm, or hbbm to form one one-dimensional (1D) chain with an oblong channel (3a) or two two-dimensional (2D) networks (1 and 6). Compound 2 or 3b consists of a dimeric [CuSCN] 2 fragment that serves either as a 4-connecting node to link the other four equivalent ones via two pairs of ebbm bridges to form a 2D (4,4) network (2) or as a 2-connecting node to bridge its two adjacent ones via a pair of prbbm bridges to form a 1D chain (3b). Compound 4 contains a new kind of [CuSCN] n double chain that is connected by bbbm with two conformations to form a unique 2D network, while 5 consists of a [CuSCN] n single chain that is linked by pbbm to form the other kind of 1D chain with an oblong channel. In addition, the photoluminescent properties of 1-6 in solid state at ambient temperature were also investigated.

Three methods have been developed to prepare gallium and indium complexes of three tetradentate N(2)S(2) ligands of the general formula M(N(2)S(2))R (M = Ga, In; R = Cl, Br, SCN, O(2)CC(6)H(5)-O,O'). The ancillary ligand (Cl, SCN, O(2)CC(6)H(5)-O,O') was varied with the tetradentate ligand BAT-TM. X-ray crystallography shows that the coordination geometry about the d(10) metal ion is influenced by the steric requirements of the ligands. X-ray crystallography of four molecules results in the following data: GaCl(BAT-TM) (1), formula = C(10)H(22)ClGaN(2)S(2), space group = Pnma, a = 12.387(4) Å, b = 21.116(6) Å, c = 5.986(2) Å, V = 1565.8(9) Å(3), Z = 4; InCl(BAT-TM) (2), formula = C(10)H(22)ClInN(2)S(2), space group = Pnma, a = 12.968(9) Å, b = 29.29(1) Å, c = 5.866(2) Å, V = 1620(2) Å(3), Z = 4; InNCS(BAT-TM) (3), formula = C(11)H(24)ClInN(3)S(3), space group = Pbca, a = 11.812(3) Å, b = 11.679(3) Å, c = 24.238(9) Å, V = 3449.7 (17) Å(3), Z = 8; In(O,O'-O(2)CC(6)H(5))(BAT-TM) (4), formula = C(19)H(29)O(2)InN(2)S(2), space group = P2(1)/n, a = 10.783(2) Å, b = 18.708(4) Å, c = 12.335(4) Å, V = 2321.7(9) Å(3), Z = 4. Proton NMR studies show that the complexes are stable in solution; in polar solvents such as acetonitrile, for certain molecules, two metal-ligand complexes are observed. Similarly, two metal-ligand complexes are seen in NMR data taken in 80% acetonitrile/20% D(2)O (pD = 4.6) mixture. HPLC studies (acetonitrile/50 mM sodium acetate, pH = 4.6) show that the lipophilicity of the ligand determines the retention time of the complex.

Reactions of Cd(NO(3))(2)·4H(2)O with TabHPF(6) (TabH = 4-(trimethylammonio)benzenethiol) and Et(3)N in the presence of NH(4)SCN and five other N-donor ligands such as 2,2'-bipyridine (2,2'-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd(2)(μ-Tab)(4)(NCS)(2)](NO(3))(2)·MeOH}(n) (1), [Cd(2)(μ-Tab)(2)(L)(4)](PF(6))(4) (2: L = 2,2'-bipy; 3: L = phen), [Cd(Tab)(2)(L)](PF(6))(2) (4: L = 2,9-dmphen; 5: L = bppy), and [Cd(2)(μ-Tab)(2)(Tab)(2)(bdmppy)](2)(PF(6))(8)·H(2)O (6·H(2)O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)](+) fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2'-bipy)(2)](2+) or [Cd(phen)(2)](2+) units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)(2)(L)](2+) dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(μ-Tab)(2)Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.