A Cyclic Alkyl(amino)carbene as Two-Atom π-Chromophore Leading to the First Phosphorescent Linear CuI Complexes
A Cyclic Alkyl(amino)carbene as Two-Atom π-Chromophore Leading to the First Phosphorescent Linear CuI Complexes
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DOI：
10.1002/chem.201605412
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发表时间：
2017-02-01
影响因子：
4.3
通讯作者：
Steffen, Andreas
中科院分区：
文献类型：
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作者：
Gernert, Markus;Mueller, Ulrich;Steffen, Andreas
与相应的N-杂环卡宾(NHC)配合物相比，一系列含有环烷(氨基)卡宾(CAAc)配体的线性和三角铜(I)配合物的成员显示出惊人的光物理性质。线型NHC络合物[Cux(NHC)]几乎不发光，而[Cux(CaAc)](X=Cl，Br，I)和[Cu(CaAc)(2)]PF6在蓝绿区域表现出从三重态激发态的非常明亮的发射，在固体中表现出高达65%的量子产率，即使pi-受体只包含没有其他pi共轭的卡宾C和N原子。[Cu(CaAc)(2)]Pf6是目前最快的铜基三重态发光体，具有不显示热激活延迟荧光的特性，其本征寿命仅为10.6亩S，即k(R)=9.4V10(4)S(-1)，与许多铂-II和Ir-III基发光体竞争。为了测试这种线性铜CAAc络合物在器件中的稳定性，我们的一些化合物已经应用于原理验证有机电致发光二极管(OLED)。这一案例研究首次证明了CAAC作为铜碘系磷光发光体的合适的发色团的用途，并且它们在有机发光二极管中的应用强调了这类配体在材料科学中的普遍适用性。
The members of a series of linear and trigonal copper(I) complexes bearing a cyclic alkyl(amino) carbene (CAAC) ligand show surprising photophysical properties compared to those of the corresponding N-heterocyclic carbene (NHC) complexes. Whereas the linear NHC complexes [CuX(NHC)] are almost non-emissive, [CuX(CAAC)] (X= Cl, Br, I) and [Cu(CAAC)(2)] PF6 show very bright emissions from their triplet excited states in the blue to green region, displaying quantum yields of up to 65% in the solid state, even though the pi-acceptor comprises only the carbene C and N atoms with no other pi conjugation. [Cu(CAAC)(2)] PF6 is the fastest Cu-I-based triplet state emitter characterized to date, not dis-playing thermally activated delayed fluorescence (TADF), with an intrinsic lifetime of only 10.6 mu s, that is, k(r)= 9.4 V 10(4) s(-1), competitive with many Pt-II-and Ir-III-based emitters. In order to test the stability of such linear copper CAAC complexes in devices, some of our compounds have been applied in proof-of-principle organic light-emitting diodes (OLEDs). This case study thus demonstrates for the first time the use of CAACs as suitable pi-chromophores for Cu-I-based phosphorescent emitters, and their implementation in OLEDs underlines the general applicability of this class of ligands in materials science.