Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands.
Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands.
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DOI：
10.1039/c2dt30618b
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发表时间：
2012-08
影响因子：
4
通讯作者：
Xiaohui Liu;Hongmei Nan;Wei Sun;Qikai Zhang;Ming Zhan;Luyi Zou;Z. Xie;Xiao Li;Canzhong Lu;Yanxiang Cheng
中科院分区：
文献类型：
--
作者：
Xiaohui Liu;Hongmei Nan;Wei Sun;Qikai Zhang;Ming Zhan;Luyi Zou;Z. Xie;Xiao Li;Canzhong Lu;Yanxiang Cheng
本发明公开了一种具有二吡咯衍生物和膦混合配体的杂配中性单核亚铜配合物，包括1，3，7，9-四甲基二吡咯（1）、5-苯基-1，3，7，9-四甲基二吡咯（2）、2，8-二溴-1，3，7，9-四甲基二吡咯（3）、1，9-二氯-5-苯基二吡咯（4）、1，9-二溴-5-苯基二吡咯（5）、5-五氟苯基-1，3，7，合成并表征了9-四甲基二吡咯（6）和1，5，9-三苯基二吡咯（7）。在通式Cu（1-6）（PPh（3））（2）（1a-6a）和Cu（1-6）（DPEphos）（1b-6 b）[DPEphos =双（2-二苯基膦基苯基）醚]中，这些配合物的中心Cu（i）原子均呈现拟四面体构型，而配合物Cu（7）（PPh（3））（7a）由于配体7的大空间位阻而呈现三配位的金字塔构型。与传统的[Cu（phen）（PP）]（+）类似物相比，Cu（i）-Cu（ii）氧化的氧化电位非常低，在0.36-1.02 V范围内（相对于Ag/AgCl）。它们的发射最大值范围为495至595 nm，在二氯甲烷中，在室温下的量子产率为0.05-4.03%和寿命的纳秒级。与阳离子Cu（i）配合物中的MLCT发射不同，基于二吡咯啉阴离子内共轭增加导致金属-配体相互作用减弱，从而阻止配体的π轨道和Cu（i）原子的3d轨道混合的事实，将发射归属于二吡咯啉中心配体内电荷跃迁（ILCT）。这一结论也得到了电化学数据和理论计算的支持。
Heteroleptic neutral mononuclear cuprous complexes with dipyrrin derivatives and phosphine mixed-ligands including 1,3,7,9-tetramethyldipyrrin (1), 5-phenyl-1,3,7,9-tetramethyldipyrrin (2), 2,8-dibromo-1,3,7,9-tetramethyldipyrrin (3), 1,9-dichloro-5-phenyldipyrrin (4), 1,9-dibromo-5-phenyldipyrrin (5), 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin (6) and 1,5,9-triphenyldipyrrin (7) have been synthesized and fully characterized. The central Cu(i) atoms of these complexes in general formulas of Cu(1-6)(PPh(3))(2) (1a-6a) and Cu(1-6)(DPEphos) (1b-6b) [DPEphos = bis(2-diphenylphosphinophenyl)ether] all exhibit a pseudo-tetrahedral geometry, while complex Cu(7)(PPh(3)) (7a) is tricoordinated in a pyramidal conformation due to the large steric hindrance of ligand 7. The oxidation potentials assigned to oxidations of Cu(i)-Cu(ii) are extraordinarily low in the range of 0.36-1.02 V vs. Ag/AgCl compared with traditional [Cu(phen)(PP)](+) analogues. Their emission maxima range from 495 to 595 nm in dichloromethane at room temperature with quantum yields of 0.05-4.03% and lifetimes on the order of nanoseconds. Unlike the characteristic MLCT emission in cationic Cu(i) complexes, the emissions are assigned to the dipyrrin-centered intraligand charge transition (ILCT) based on the fact that the increased conjugation within the dipyrrinato anion leads to a weaker metal-ligand interaction, thus preventing the mixing of π orbitals of ligand and 3d orbitals of Cu(i) atom. This conclusion is also supported by electrochemical data and theoretical calculations.