| In this thesis, nine novel copper(I) oligomers and polymers have been synthesized by reaction of copper(I) halide and pseudo halide with heterocyclic thiones, [Cu4(pymtH)4Cl4]n (1), [Cu4(pymtH)4Br4]n (2), [Cu(pymtH)2I]2 (3), [Cu(μ3- H3TMT)Cl]n (4), [Cu(μ3-H3TMT)Br]n (5), [Cu(μ3-H3TMT)I]n (6), [(CuSCN)(2-pds)0.5]n(7), [(CuSCN)(2-pmds)]n (8), [(CuI)2(2-pmds)]2(9). These complexes have been characterized by elemental analyses (EA), infrared spectra (IR), thermogravimetric analysis (TGA), X-ray single crystal diffraction, and fluorescence spectroscopic analyses.The complex [Cu4(pymtH)4Cl4]n 1 crystalizes in the triclinic space group pi, v/ith a = 7.4760(6) A, b = 7.5128(6) A, c = 12.9983(11) A, α = 83.0860(10)°, β = 81.8930(10)°, γ = 62.8890(10)°, V = 642.04(9) A3, Z = 1, Dc = 2.184 Mg/m3. The single crystal determination for complex 1 reveals that ligands pymtH act as bridging ligand with two kinds of coordination modes: μ2-(S,N) and μ3-(S2N). Two ligands bridge CuI in coordination mode μ3-(S2N) giving a centrosymmetric 8-membered (CuSCN)2 ring, another two ligands adopting bridging mode μ2-(S,N) bridge two adjacent Cu4 building-block unit to form a centrosymmetric 16-membered (CuSCN)4 ring. The 8-membered ring and 16-membered ring arrange alternately along the crystallographic a-direction to construct a 1D chain polymer. All Cl atoms are terminally coordinated to CuI. The Cu centers have two different coordination environments in the complex, that is, CuNSCl in a distorted planar trigonal geometry, and CuNS2Cl in a distorted tetrahedral geometry.The complex [Cu4(pymtH)4Br4]n 2 crystalizes in the triclinic space group pi, with a = 7.4238(8) A, b = 7.5749(8) A, c = 13.4896(15) A, a = 83.579(2)°, β = 81.452(2)°, γ = 63.055(2)°, V = 667.87(13) A3, Z = 1, Dc= 2.542 Mg/m3. The single crystal determination shows that Complexes 1 and 2 are isostructural. Ligands pymtH act as bridging ligand with two kinds of coordination modes: μ2-(S,N) and μ3-(S2N). Two ligands bridge CuI in coordination mode μ3-(S2N) giving a centrosymmetric 8-membered (CuSCN)2 ring, another two ligands adopting bridging mode μ2-(S,N) bridge two adjacent Cu4 building-block unit to form a centrosymmetric 16-membered (CuSCN)4 ring. The 8-membered ring and 16-membered ring arrange alternately along thecrystallographic a-direction to construct a ID chain polymer. All Br atoms are terminally coordinated to Cu1. The Cu centers have two different coordination environments in the complex, that is, CuNSBr in a distorted planar trigonal geometry, and CuNS2Br in a distorted tetrahedral geometry.The complex [Cu(pymtH)2l]2 3 crystalizes in the orthorhombic space group Fdd2, with a = 12.8302(10) A,b = 38.855(3) A, c = 9.9562(8) A, a = 90°, p = 90°, y = 90°, V = 4963.3(7) A3, Z = 8, Dc= 2.220 Mg/m3. The complex 3 was structurally characterized as a dimmer, which is markedly different from polymers 1 and 2. In 3, the neutral pymtH with both nitrogen and sulfur as potential donating atoms adopted the monodentate coordination mode, binding the metal centers exclusively through the exocyclic sulfur atom in terminal and bridging modes. Two Cu1 are doubly bridged by two S atoms of pymtH ligands to form an asymmetric non-planar CU2S2 core. The distorted tetrahedral coordination around each Cu1 is completed by a teiminal I atom.The complex [Cu(|X3-H3TMT)Cl]n 4 crystalizes in the cubic space group Pa-3, with a = 11.7472(4) A, b = 11.7472(4) A, c = 11.7472(4) A, a = 90.00°, p = 90.00°, ; = 90.00°, V = 1621.07(10) A3, Z = 8, Dc = 2.264 Mg/m3. The single crystal X-ray diffraction study reveals complex 4 is a 3-D polymer. Each Cu1 in 4 is coordinated by three different H3T.MT ligands and, in turn, each H3TMT ligand acts as a U3 bridge linking three Cu1 through its suliur atom. Such a coordination mode generates Cu1 complexes consisting of two independent three-dimensional (3D) networks which are enantiometric and interpenetrating. In all complexes the ligands are present in the thione form, and all Cl atoms are terminally coordinated to each Cu1.The complex [Cu(u3-H3TMT)Br]? 5 crystalizes in the cubic space group Pa-3, with a = 11.8847(3) A, b = 11.8847(3) A, c = 11.8847(3) A, a = 90.00°, fi = 90.00°, y = 90.00°, V = 1678.67(7) A3, Z = 8, Dc= 2.538 Mg/m3. The single crystal X-ray diffraction study reveals that Complexes 4 and 5 are isostructural. Each Cu1 is coordinated by three S atoms of three distinct H3TMT ligands, and each H3TMT acts as a tridentate bridging ligand linking three Cu1 through its sulfur atoms. Such a coordination mode generates Cu1 complexes consisting of two independent three-dimensional (3D) networks which are enantiometric and inteipenetrating. In all complexes the ligands are present in the thione form, and all Br atoms are terminally coordinated to each Cu!.The complex [Cu(p.3-H3TMT)I]n 6 crystalizes in the cubic space group Pa-3, with a = 12.0266(4) A, b = 12.0266(4) A, c = 12.0266(4) A, a = 90.00°, fi = 90.00°, y = 90.00°, V = 1739.52(10) A3, Z = 8, Dc= 2.808 Mg/m3. The single crystal X-ray diffraction study reveals that Complexes 4, 5 and 6 are isostructural. Each Cu1 is coordinated by three S atoms of three distinct H3TMT ligands, and each H3TMT acts as a tridentate bridging ligand linking three Cu1 through its sulfur atoms. Such a coordination mode generates Cu1 complexes consisting of two independent three-dimensional (3D) networks which are enantiometric and interpenetrating. In all complexes the ligands are present in the thione form, and all I atoms are terminally coordinated to each Cu1.The complex [(CuSCN)(2-pds)o.s]w 7 crystalizes in the orthorhombic space group Pccn, with a = 14.5076(14) A, b = 12.0266(4) A, c = 10.5013(10) A, a = 90.00°, ft = 90.00°, y = 90.00°, V = 1589.8(3) A3, Z = 8, Dc= 1.937 Mg/m3. The single crystal X-ray diffraction study reveals that Complexes 7 is a 2D polymer. Each Cu1 is coordinated by two different thiocyanato S donors, one N-donor from a third SCN" group and one 2-pds N-donor. Two infinite nearly coplanar square-wave [CuSCN],, single-stranded chains are formed through bridging SCN' groups. The crest in one chain is opposite to the trough in another chains. S atoms (crest or trough) in one chain is further coordinated to neighboring Cu atoms (crest or trough) in another chain with slightly longer Cu-S distance of 2.5053(10) A, thus novel [CuSCN],, double-stranded chain formed. [CuSCN],, double-stranded chains are further inter-connected through 2-pds ligands using two different conformations (the P- and M-form) alternately that bridge copper centers to generate a 2D network structure.The complex [(CuSCN)(2-pmds)]w 8 crystalizes in the monoclinic space group P2(l)/c, with a = 8.502(2) A, b = 14.079(3) A, c = 11.170(4) A, a = 90.00°, fi = 110.69(2)°, y = 90.00°, V = 1250.8(6) A3, Z = 12, Dc= 1.826 Mg/m3. The single crystal X-ray diffraction study reveals that Complexes 7 is a 2D polymer. Each Cu central exhibits a N3S coordination sphere using two 2-pmds ligands and two SCN" groups in a distorted tetrahedral environment. SCN" groups bridge Cu1 to form zigzag [CuSCN]n single-strand chains. 2-pmds ligands with two different conformations (the P- and M-form) bridge [CuSCN]w chains alternately to forrm a 2D network structure. As the edges, two ligands and two SCN' groups form a 22-membered macrometallacyclic ring made up of four Cu1 at the corners.The complex [(Cul)2(2-pmds)]2 9 crystalizes in the monoclinic space group P2(l)/n, with a = 10.690(2) A, b = 10.690(2) A, c = 13.539(3) A, a = 90.00°, p = 113.20(3)°, y = 90.00°, V = 1452.7(5) A3, Z = 2, Dc= 2.758 Mg/m3. The single crystal X-ray diffraction study reveals that complexes 9 is centrosymmetric tetranuclear complex. Four I atoms act as \i2 and p.3 bridging modes link four Cu atom forming stair [Cul]4 conformation. In contrast to 8, each ligand 2-pmds adopts a U3-(SN2) bridging mode linking two Cu1. Such structural arrangement affords Cu centers two different coordination environments in this complex, which are, CuNSk and CUNI3 distorted tetrahedral geometry.
|
PDF Full Text Request