新型四硫富瓦烯-吡啶型半导体材料的制备、晶体结构及电学性能表征

本文利用配位驱动自组装方法在溶液中合成了一类新型的四硫富瓦烯(TTF)-吡啶-铜(Ⅰ)配合物[Cu~Ⅰ(L1)_4](ClO_4)_2,(L1=4-ethylenedithiotetrathiafulvalenylpyridine),并对其微晶和单晶的结构进行表征。通过元素分析、红外光谱和X射线衍射分析确定了该配合物晶体纯度与晶体结构。发现该配合物可通过S…S非共价相互作用组装成三维超分子网络,并且其超分子链[Cu(L1)_4]_∞沿c轴(8. 05×7. 67?)可形成一维微孔骨架。由于该配合物沿c轴方向可构建一维均匀的TTF~(+1/4)阵列,其具有较好的半导体特性,电导σ_(rt)与活化能E_a分别为9. 1×10~(-2)S·cm~(-1)和50 me V。     

Spectral and structural studies of nickel(II) complexes of salicylaldehyde 3-azacyclothiosemicarbazones

Mononuclear nickel(II) complexes with two ONS donor thiosemicarbazone ligands {salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone [H₂L¹] and salicylaldehyde 3-tetramethyleneiminyl thiosemicarbazone [H₂L²]} have been prepared and physico-chemically characterized. IR and electronic spectra of the complexes have been obtained. The thiosemicarbazones bind to the metal as dianionic ONS donor ligands in all the complexes except in [Ni(HL¹)₂] (1). In compound 1, the ligand is coordinated as a monoanionic (HL⁻) one. The magnetic susceptibility measurements indicate that all the complexes are mononuclear and are diamagnetic. The complexes were given the formulae [Ni(HL¹)₂] (1), [NiL¹py] (2), [NiL¹α-pic] (3), [NiL¹γ-pic] · H₂O (4), [NiL²py] (5) and [NiL²γ-pic] (6). The structures of compounds 2 and 3 have been solved by single crystal X-ray crystallography and were found to be distorted square planar in geometry with coordination of azomethine nitrogen, thiolato sulfur, phenolato oxygen and pyridyl nitrogen atoms.     

Synthesis and spectral characterization of zinc(II) complexes of N(4)-substituted thiosemicarbazone derived from salicylaldehyde: Structural study of a novel –OH free Zn(II) complex

Five novel zinc(II) complexes of salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone were synthesized and physico-chemically characterized. The complexes were given the formulae [Zn(HL)₂] (1), [Zn(L)py] (2), [Zn(L)bipy] · 3.5H₂O (3), [Zn(L)phen] · H₂O (4) and [Zn(L)γ-pic] (5). The thiosemicarbazone binds the metal as a dianionic ONS donor ligand in all the complexes, except in 1. Compound 1 is a homoleptic complex with zinc occupying the center of a distorted tetrahedral environment and being coordinated by two azomethine nitrogen and two thiolate sulfur atoms.     

Spectral and structural studies of copper(II) complexes of thiosemicarbazones derived from salicylaldehyde and containing ring incorporated at N(4)-position

Mononuclear and binuclear copper(II) complexes (1-8) with two ONS donor thiosemicarbazone ligands {salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone [H2L1] and salicylaldehyde 3-tetramethyleneiminyl thiosemicarbazone [H2L2]} have been prepared and physico-chemically characterized. IR, electronic and EPR spectra of the complexes have been obtained. The thiosemicarbazones bind to metal as dianionic ONS donor ligands in all the complexes except in [Cu(HL1)2] (2) and [Cu(HL2)2] (6). In compounds 2 and 6 the ligands are coordinated as monoanionic HL- ones. The magnetic susceptibility measurements indicate that all the complexes are paramagnetic. In complex [(CuL1)2] (1), the magnetic moment value is lower than the expected spin only value. In all the complexes g(||)>g( perpendicular)>2.0023 and G values within the range 2.5-3.5 are consistent with dx2-y2 ground state. The complexes were given the formula as [(CuL1)2] (1); [Cu(HL1)2] (2); [CuL1bpy] (3); [CuL1phen] (4); [CuL1gamma-pic].2H2O (5); [Cu(HL2)2] (6); [CuL2py].3H2O (7); [CuL2bipy] (8). The structure of the compound 8 have been solved by single crystal X-ray crystallography and was found to be distorted square pyramid around copper(II) ion.     

Salicylaldehyde 4,4′‐(hexane‐1,6‐di­yl)­thio­semicarbazone

The title compound, C₁₄H₁₉N₃OS, is in the thio­keto form, with the thione S and hydrazine N atoms cis with respect to each other so that the S atom is involved in inter‐ and intra­molecular hydrogen bonds simultaneously. Inter­molecular C—H⋯S and C—H⋯O hydrogen bonds result in one‐dimensional polymeric chains of mol­ecules along the a axis. A weak C—H⋯π ring inter­action binds the polymeric chains together.