Synthesis And Characterization Of Bipyridyl Tetrazolium Copper (I) Complexes

Copper???complexes have recently become a focus of coordination chemistry research because of their rich structures and wide applications,especially their promising application prospects in the optical function materials.In this thesis,twelve Cu???complexes have been synthesized by the structural modification of bipyridyl-tetrazole ligands and the variation of phosphine auxiliaries.The structural features of these Cu???complexes and the coordination modes of the ligands have been characterized and investigated by single-crystal X-ray diffraction,elemental analysis,IR spectroscopy,1H and 31 P NMR spectroscopies and UV-vis absorption spectroscopy.1.Two trinuclear Cu???clusters [Cu₃?tbpy?₂?PPh3?₃)]?ClO₄??1?and[Cu₃?tmbpy?₂?PPh3?₃]?ClO₄??2?as well as two tetranuclear Cu???clusters[Cu₄?tbpy?₂?dppm?4]?ClO₄?₂?3?and [Cu₄?tmbpy?₂?dppm?4]?ClO₄?₂?4?,have been synthesized by using two bipyridyl-tetrazole ligands?tbpyH = 6-?1H-tetrazol-5-yl?-2,2'-bipyridine,tmbpyH = 6-?1H-tetrazol-5-yl?-4,4'-dimethyl-2,2'-bipyridine?.Single-crystal structural analysis shows that the structures of complexes 1 and 2 are almost similar,and three Cu???atoms adopt two kinds of coordination fashions,where the Cu₁ and Cu₂ atoms adopt a four-coordinate mode and form an N₃ P distored tetrahedral geometry,whereas the Cu₃ atom takes a three-coordinate mode and generate an N₂ P planar triangle.The Cu₁ and Cu₂ atoms of3 are three and four coordinated,respectively,whereas the Cu???atoms of 4 are all four coordinated.The tbpyH and tmbpyH ligands display three different coordination modes as tridentate and tetradentate ligand in 1–4.It is shown that the methylation of the bipyridyl ring and the alteration of phosphine ligands have a significant effect on the structures of the resulting Cu???complexes and the coordination modes of the bipyridyl-tetrazole ligands.2.Using above two bipyridyl-tetrazole ligands?tbpyH and tmbpyH?,four alkylated bipyridyl-tetrazole ligands?etbpy = 6-?1-ethyl-tetrazol-5-yl?-2,2'-bipyridine,htbpy = 6-?1-hexyl-tetrazol-5-yl?-2,2'-bipyridine,2-etbpy = 6-?2-ethyl-5-tetrazolyl?-2,2?-bipyridine,and2-etmbpy = 6-?2-ethyl-5-tetrazolyl?-4,4?-dimethyl-2,2?-bipyridine?have been synthesized via the NH-alkylation reaction of the tetrazolyl ring.These four ligands are used to construct four Cu???complexes,including two binuclear Cu???complexes [Cu₂?etbpy?₂?PPh₃?₂]?ClO₄?₂?5?and [Cu₂?htbpy?₂?PPh₃?₂]?ClO₄?₂?6?and two mononuclear Cu???complexes[Cu?2-etbpy??PPh3?₂)]?ClO₄??7?and [Cu?2-etmbpy??PPh3?₂)]?ClO₄??8?.Complexes 5 and 6show similar structures,and each Cu???atom shows an N₃ P distorted tetrahedral environment.For 7 and 8,the Cu???atoms display an N₂P2 distorted tetrahedral configuration.Four ligands?etbpy,htbpy,2-etbpy,and 2-etmbpy?in 5–8 show two different tridentate coordination fashions serve as tridentate and didentate ligand.It is shownt that the NH-alkylation of the tetrazolyl ring have an important effect on the structures of Cu???complexes and the coordination mode of the ligands,whereas the variation of the alkyl groups on the tetrazolyl ring only slightly affects the distortion of the tetrahedral geometry.3.Using two NH-ethylated bipyridine-tetrazole ligands?2-etbpy and 2-etmbpy?and two different carbon chain length of disphosphine ligands?bis?diphenylphosphino?methane?dppm?and 1,3-bis?diphenylphosphino?propane?dppp??,two binuclear Cu???complexes[Cu₂?2-etbpy??Me CN??dppm?₂]?ClO₄?₂?9?and [Cu₂?2-etmbpy??MeCN??dppm?₂]?ClO₄?₂?10?and two mononuclear Cu???complexes [Cu?2-etbpy??dppp?]?ClO₄??11?and[Cu?2-etmbpy??dppp?]?ClO₄??12?have been afforded.Two Cu???atoms of 9 and 10 respectively adopt the N₂ P and N₂P₂ coordination modes and they are bridged by two dppm ligands to form an eight-member cyclic structure.All the Cu???atom of 11 and 12 display an N₂P₂ distorted tetrahedral configuration.Two ligands of 9–12 exhibit only one bidentate coordination mode.It is shown that the different carbon chain length of disphosphine ligands have a certain influence of the structures of Cu???complexes,whereas it has no remarkable effect on the coordination mode of the bipyridyl-tetrazole ligands.