合成并表征了2个新的基于6-甲氧羰基-4,4'-二甲基-2,2'-联吡啶的单核铜(Ⅰ)双膦配合物[Cu(mmbpy)(dppp)]ClO4(1)和[Cu(mmbpy)(dppb)]ClO4(2).研究结果表明,铜(Ⅰ)配合物1和2均表现为扭曲变形的N2R四面体几何构型,其P-Cu-P键角受辅助双膦配体控制.在常温下,这2个铜(Ⅰ)配合物在固态时均具有发光性质,并且相对于双膦配体亚甲基链的长度,P-Cu-P键角对其光物理性质的影响更为显著.在2,2'-联毗啶环上引入2个甲基取代基对改善铜(Ⅰ)配合物的发光性能也被证明是有效的.%Two new mononuclear copper(Ⅰ) diphosphine complexes based on 6-methoxycarbonyl-4,4'-dimethyl2,2'-bipyridine (mmbpy),[Cu(mmbpy)(dppp)]ClO4 (1) and [Cu(mmbpy)(dppb)]ClO4 (2),have been synthesized and characterized.It is revealed that Cu(Ⅰ) complexes 1 and 2 all exhibit distorted N2P2 tetrahedral geometries with varied P-Cu-P angles regulated by auxiliary diphosphine ligands.The two Cu(Ⅰ) complexes are all emissive in the solid state at ambient temperature,and their photophysical properties are more markedly influenced by the P-CuP angle than the methylene chain length of diphosphine.It is also demonstrated that the introduction of two methyl substituents into the 2,2'-bipyridyl ring is effective for improving luminescence properties of Cu(Ⅰ)complexes.CCDC:1543374,1;1543375,2.
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