Synthesis, Characterization And Photophysical Properties Of Pyridinium Copper (I) Complexes

Cu(I)complexes have a variety of structures,excellent luminescence properties,controllable structures and promising potential applications in the fields of optical materials and communication equipments,therefore they have made to be one of the best luminescent materials.In this thesis,we have synthesized three kinds of NH-containing pyridyl azole,including pyridyl-pyrazole,pyridyl-triazole and pyridyl-benzimidazole,and series of pyridyl-azole-based Cu(I)complexes have been also prepared by using various phosphine ligands.The structures and photophysical properties of these as-synthesized Cu(I)complexes have been investigated by X-ray single-crystal diffraction,infrared spectroscopy,UV-vis absorption spectroscopy,mass spectroscopy,NMR spectroscopy,fluorescence spectroscopy and TD-DFT calculation.1.Three neutral mononuclear Cu(I)complexes([Cu(PPh3)2(p-mpftz)](1),[Cu(PPh3)2(m-mpftz)](2)and [Cu(PPh3)2(o-mpftz)](3))and two ionic mononuclear Cu(I)complexes([Cu(PPh3)2(p-mpftzH)](ClO4)(4)and [Cu(PPh3)2(m-mpftzH)](ClO4)(5))have been synthesized via the reaction of [Cu(PPh3)2(MeCN)2](ClO4)and three different positions of pyridyl-azole ligands under diverse conditions.The structures and photophysical properties of these Cu(I)complexes 1-4 have been measured and studied.It is shown that the deprotonation of the 1,2,4-triazolyl-NH not only leads to the inversion of 1,2,4-triazolyl ring,but also has a significant influence on the structures and luminescence properties of Cu(I)complexes.2.A series of mononuclear and dinuclear Cu(I)complexes,[{Cu(Hbmp)}2(?-dppm)2](ClO4)2(6),[Cu(Hbmp)(dppe)](ClO4)(7),[Cu(Hbmp)(dppp)](ClO4)(8),[Cu(Hbmp)(DPEphos)](ClO4)(9),[Cu(Hbmp)(xantphos)](ClO4)(10)and[Cu(Hbmp)(dppf)](ClO4)(11),have been synthesized by using2-(2'-benzimidazolyl)-6-methylpyridine and diphosphine mixed ligands.The structures and luminescence properties of 6-11 have been investigated.It is shown that the P–Cu–P angles have more significant effects on the photophysical properties of Cu(I)complexes than the electronic properties of the diphosphine.3.Three dppb-bridged dinuclear Cu(I)complexes,[{Cu(pypzH)}2(?-dppb)2](ClO4)2(12),[{Cu(pybzH)}2(?-dppb)2](ClO4)2(13),and [{Cu(pyfz H)}2(?-dppb)2](ClO4)2(14),have been synthesized by using three different pyripyl-pyrazole ligands including 3-(2'-pyridyl)pyrazole(pypz H),5-tert-butyl-3-(2'-pyridyl)pyrazole(pybzH)and 5-trifluoromethyl-3-(2-pyridyl)pyrazole(pyfz H).The structures and photophysical properties of 12-14 have been investigated.It is shown that the introduction of different substituents into the pyrazolyl ring has great influence on the luminescence properties.The introduction of electron-withdrawing groups into the pyrazolyl will effectively enhance the luminescence properties of the resulting Cu(I)complexes,whereas theintroduction of electron-donating groups will markedly decrease the luminescence properties of Cu(I)complexes.