Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub-Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties
Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub-Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties
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DOI：
10.1002/chem.201605891
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发表时间：
2017-04-03
影响因子：
4.3
通讯作者：
Bochmann, Manfred
中科院分区：
文献类型：
--
作者：
Romanov, Alexander S.;Becker, Ciaran R.;Bochmann, Manfred
由甲基、乙基和金刚烷基取代的环状（烷基）（氨基）卡宾（CAAC）配体稳定的铜和金的卤化物和拟卤化物络合物大多是固态的线性单体，没有亲金AuAu相互作用。 (L-Et2)CuCl 显示出该系列中最高的光致发光量子产率 (PLQY)，为 70%。 L-Me2 和 L-Et2 卤化铜配合物的光发射显示出 ns 时间尺度的 S1S0 荧光，与理论一致，并且发射寿命长。单体 (L-Me2)CuNCS 是一种白色发射体，而二聚体 [(L-Et2)Cu(-NCS)](2) 显示出强烈的黄色发射，光致发光 (PL) 量子产率为 49%。 (L-Ad)MCl (M=Cu 或 Au) 与酚类 ArOH (Ar=Ph, 2,6-F2C6H3, 2,6-Me2C6H3, 3,5-tBu(2)C(6)H(3), 2-tBu-5-MeC6H3, 2-吡啶基)、苯硫酚或芳香胺 H2NAr (Ar=Ph, 3,5-(CF3)(2)C6H3,C6F5,2-py)得到相应的酚基、苯硫酚基和酰胺基络合物。尽管发射波长仅受环取代模式的轻微影响，但 PL 强度对邻位或间位取代基的存在敏感响应。在金芳氧化物中，PL 受空间因素控制，在具有 Au-O-C-C 扭转角的化合物中具有强发光
Copper and gold halide and pseudo-halide complexes stabilised by methyl-, ethyl- and adamantyl-substituted cyclic (alkyl)(amino)carbene (CAAC) ligands are mostly linear monomers in the solid state, without aurophilic AuAu interactions. (L-Et2)CuCl shows the highest photoluminescence quantum yield (PLQY) in the series, 70%. The photoemissions of L-Me2 and L-Et2 copper halide complexes show S1S0 fluorescence on the ns time scale, in agreement with theory, as well as a long-lived emission. Monomeric (L-Me2)CuNCS is a white emitter, whereas dimeric [(L-Et2)Cu(-NCS)](2) shows intense yellow emission with a photoluminescence (PL) quantum yield of 49%. The reaction of (L-Ad)MCl (M=Cu or Au) with phenols ArOH (Ar=Ph, 2,6-F2C6H3, 2,6-Me2C6H3, 3,5-tBu(2)C(6)H(3), 2-tBu-5-MeC6H3, 2-pyridyl), thiophenol, or aromatic amines H2NAr (Ar=Ph, 3,5-(CF3)(2)C6H3, C6F5, 2-py) afforded the corresponding phenolato, thiophenolato and amido complexes. Although the emission wavelengths are only marginally affected by the ring substitution pattern, the PL intensities respond sensitively to the presence of substituents in the ortho or meta positions. In gold aryloxides, PL is controlled by steric factors, with strong luminescence in compounds with Au-O-C-C torsion angles