A series of luminescent dinuclear mixed-valence gold alkynyl complexes,[(tBuC^N^CtBu)Au^(Ⅲ)(CuC)-AuⅠ(PPh3)],[(RC^N^CR)Au^(Ⅲ)(CuCCuC)Au^(Ⅰ)(PPh3)](R=H,tBu),[(RC^N^CR)Au^(Ⅲ)(CuCC6H4CuC)Au^(Ⅰ)(PPh3)](R=H,tBu),and[(...A series of luminescent dinuclear mixed-valence gold alkynyl complexes,[(tBuC^N^CtBu)Au^(Ⅲ)(CuC)-AuⅠ(PPh3)],[(RC^N^CR)Au^(Ⅲ)(CuCCuC)Au^(Ⅰ)(PPh3)](R=H,tBu),[(RC^N^CR)Au^(Ⅲ)(CuCC6H4CuC)Au^(Ⅰ)(PPh3)](R=H,tBu),and[(RC^N^CR)Au^(Ⅲ)(CuCC6H4CuC)Au^(Ⅰ)(P(C6H4R’-p)3)](R=H;R’=OMe,Cl)as well as the precursor complexes,[Au^(Ⅲ)(tBuC^N^CtBu)(CuCSiMe3)]and[Au^(Ⅲ)(tBuC^N^CtBu)(CuCH)],have been synthesized and their electrochemical properties have been investigated.The molecular structures of a number of dinuclear mixed-valence gold alkynyl complexes have been determined by X-ray crystallography.For complexes with a butadiynyl bridge,the emission was derived from an admixture of metalperturbed triplet intraligand(3IL)[π-π^(*)(RC^N^CR)]and[π-π^(*)(CuC-CuC)]states while for complexes with a 1,4-diethynylbenzene bridge,the emission was assigned as derived from the excited state of the 3IL[π→π^(*)(CuCC6H4CuC)]origin.Computational studies have also been performed for selected complexes to support the assignment of the spectroscopic origin and the nature of the photophysical properties.展开更多
基金supported by the French National Research Agency(ANR)/Research Grants Council(RGC)Joint Research Scheme(A-HKU704/12)the Research Grants Council Theme-Based Research Scheme(TBRS)(T23-713/11)of the Hong Kong Special Administrative Region.
文摘A series of luminescent dinuclear mixed-valence gold alkynyl complexes,[(tBuC^N^CtBu)Au^(Ⅲ)(CuC)-AuⅠ(PPh3)],[(RC^N^CR)Au^(Ⅲ)(CuCCuC)Au^(Ⅰ)(PPh3)](R=H,tBu),[(RC^N^CR)Au^(Ⅲ)(CuCC6H4CuC)Au^(Ⅰ)(PPh3)](R=H,tBu),and[(RC^N^CR)Au^(Ⅲ)(CuCC6H4CuC)Au^(Ⅰ)(P(C6H4R’-p)3)](R=H;R’=OMe,Cl)as well as the precursor complexes,[Au^(Ⅲ)(tBuC^N^CtBu)(CuCSiMe3)]and[Au^(Ⅲ)(tBuC^N^CtBu)(CuCH)],have been synthesized and their electrochemical properties have been investigated.The molecular structures of a number of dinuclear mixed-valence gold alkynyl complexes have been determined by X-ray crystallography.For complexes with a butadiynyl bridge,the emission was derived from an admixture of metalperturbed triplet intraligand(3IL)[π-π^(*)(RC^N^CR)]and[π-π^(*)(CuC-CuC)]states while for complexes with a 1,4-diethynylbenzene bridge,the emission was assigned as derived from the excited state of the 3IL[π→π^(*)(CuCC6H4CuC)]origin.Computational studies have also been performed for selected complexes to support the assignment of the spectroscopic origin and the nature of the photophysical properties.
