Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands
文献类型：期刊论文
| 作者 | Liu, Xiaohui2,3; Nan, Hongmei1; Sun, Wei2,4; Zhang, Qikai4; Zhan, Mingjian2; Zou, Luyi2; Xie, Zhiyuan2; Li, Xiao2; Lu, Canzhong4; Cheng, Yanxiang2 |
| 刊名 | DALTON TRANSACTIONS
 |
| 出版日期 | 2012 |
| 卷号 | 41期号:34页码:10199-10210 |
| ISSN号 | 1477-9226 |
| DOI | 10.1039/c2dt30618b |
| 英文摘要 | 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)-(PPh3)(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)(PPh3) (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 pi orbitals of ligand and 3d orbitals of Cu(I) atom. This conclusion is also supported by electrochemical data and theoretical calculations. |
| 语种 | 英语 |
| WOS记录号 | WOS:000307306400014 |
| 出版者 | ROYAL SOC CHEMISTRY |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/49213]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Nan, Hongmei |
| 作者单位 | 1.Changchun Univ Chinese Med, Affiliated Hosp 1, Changchun 130021, Peoples R China 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 3.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China 4.Chinese Acad Sci, State Key Lab Struct Chem, Fujian Inst Res Struct Matter, Fuzhou 350002, Peoples R China |
| 推荐引用方式 GB/T 7714 | Liu, Xiaohui,Nan, Hongmei,Sun, Wei,et al. Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands[J]. DALTON TRANSACTIONS,2012,41(34):10199-10210. |
| APA | Liu, Xiaohui.,Nan, Hongmei.,Sun, Wei.,Zhang, Qikai.,Zhan, Mingjian.,...&Cheng, Yanxiang.(2012).Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands.DALTON TRANSACTIONS,41(34),10199-10210. |
| MLA | Liu, Xiaohui,et al."Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands".DALTON TRANSACTIONS 41.34(2012):10199-10210. |
入库方式： OAI收割
来源：化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。