Synthesis And Characterization Of Luminescent Multinuclear Cu(I)-Diphosphine-1H-Imidazo [4,5-f][1,10]Phenanthroline Complexes

The copper(I)-diphosphine-imine complexes display good luminescent properties,and Cu(I)ion possess the advantages of low toxicity,abundant resource and low cost,so the copper(I)-diphosphine-imine complexes can be used to replace precious metals complexes in the research of organic light-emitting diodes(OLEDs),luminous electrochemical cells(LEC)and other organic light-emitting materials and devices,however,their corresponding systems mainly focused on mononuclear Cu(I)complexes,multinuclear cuprous-diphosphine-imine and Cu(I)/Cu(II)mixed-valence complexes received few attention so far.On the other hand,multinuclear Cu(I)complexes have unique luminescent properties,and Cu(I)/Cu(II)mixed-valence complexes show important catalytic activity in organisms.Meanwhile,1H-imidazo[4,5-f][1,10]phenanthroline ligands are a class of bridging ligands with multiple coordination sites for rational design and synthesis of the above-mentioned complexes,therefore,the multinuclear cuprous-diphosphine-1H-imidazo[4,5-f][1,10]phenanthroline complexes are selected as studying objects in this thesis.There are mainly four parts in this thesis:The concepts,construction,classification and application of multinuclear metal complexes,multinuclear cuprous complexes and mixed-valence copper complexes are reviewed in the 1st chapter.In the 2nd chapter,three 1H-imidazo[4,5-f][1,10]phenanthroline ligands with multi-coordination sites were synthesized first,and then three binuclear [Cu2(L-H)(xantphos)2]ClO4 and three trinuclear [Cu3(L-2H)(xantphos)3]ClO4 complexes were rationally designed and synthesized by reaction of [Cu(MeCN)4]ClO4 with these 1H-imidazo[4,5-f][1,10]phenanthroline ligands and the bulky,rigid chelating diphosphine ligand 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene(xantphos).The crystal structures of these complexes and their luminescent properties were studied.Both trigonal planar and tetrahedral coordination modes of Cu(I)centers were observed for these complexes,and they exhibit obvious C-H???Cu agostic or anagostic interaction for the trigonal planar Cu(I)centers.Four complexes of Cu(I)/Cu(II)mixed-valence complexes containing free coordination sites with diphosphine and 1H-imidazo[4,5-f][1,10]phenanthroline as ligands were synthesized,and their structures and photophysical properties were studied in the 3rd chapter.Three pentatrinuclear Cu(I)/Cu(II)mixed-valence complexes with diphosphine and 1H-imidazo[4,5-f][1,10]phenanthroline as ligands were synthesized in the 4th chapter,and their structures and photophysical properties were studied.