Emission Tuning of Luminescent Copper(I) Complexes by Vapor-Induced Ligand Exchange Reactions.
Emission Tuning of Luminescent Copper(I) Complexes by Vapor-Induced Ligand Exchange Reactions.
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DOI：
10.1021/acs.inorgchem.6b03122
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发表时间：
2017-04
影响因子：
4.6
通讯作者：
T. Hasegawa;A. Kobayashi;H. Ohara;Masaki Yoshida;Masako Kato
中科院分区：
文献类型：
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作者：
T. Hasegawa;A. Kobayashi;H. Ohara;Masaki Yoshida;Masako Kato
合成了两个发光的单核Cu（I）配合物[Cu（PPh_2Tol）（THF）（4M_3）_2]（BF_4）（1）和[Cu（PPh_2Tol）（4M_3）_3]（BF_4）（2）（PPh_2Tol =二苯基邻甲苯基膦，4-甲基吡啶，THF =四氢呋喃），研究了它们的晶体结构、发光性质和固相气相诱导配体交换反应.两个配合物都是四面体，但配合物2的三个4 Mepy配体中的一个被配合物1中的四氢呋喃溶剂分子取代。与室温下固体状态下THF结合的配合物1的非常弱的蓝色发射（发射最大波长（λem）= 457 nm，发射量子产率（Φem）= 0.02）相反，观察到2的非常明亮的蓝绿色发射（λem = 484 nm，Φem = 0.63），表明THF配体对非辐射失活的贡献。含时密度泛函理论计算和发射寿命的测量表明，室温下的配合物的发射是由于热激活延迟荧光从金属到配体的电荷转移激发态。有趣的是，通过暴露固体样品的THF结合的1至4兆焦耳蒸汽，发射强度急剧增加，发射颜色从蓝色变成蓝绿色。粉末X-射线衍射测量表明，1的发射变化是由于蒸汽诱导的配体交换的THF为4 M3，形成强发射的配合物2。通过将1暴露于嘧啶或吡嗪蒸气，分别形成绿色（λem = 510 nm）或橙子（λem = 618 nm）发射复合物，实现进一步的发射调谐。这些结果表明，气相诱导配体交换是一种很有前途的控制发光Cu（I）配合物发光颜色的方法。
We have synthesized two luminescent mononuclear Cu(I) complexes, [Cu(PPh2Tol)(THF)(4Mepy)2](BF4) (1) and [Cu(PPh2Tol)(4Mepy)3](BF4) (2) (PPh2Tol = diphenyl(o-tolyl)phosphine, 4Mepy = 4-methylpyridine, THF = tetrahydrofuran), and investigated their crystal structures, luminescence properties, and vapor-induced ligand exchange reactions in the solid state. Both coordination complexes are tetrahedral, but one of the three 4Mepy ligands of complex 2 is replaced by a THF solvent molecule in complex 1. In contrast to the very weak blue emission of the THF-bound complex 1 (wavelength of emission maximum (λem) = 457 nm, emission quantum yield (Φem) = 0.02) in the solid state at room temperature, a very bright blue-green emission was observed for 2 (λem = 484 nm, Φem = 0.63), suggesting a contribution of the THF ligand to nonradiative deactivation. Time-dependent density functional theory calculations and emission lifetime measurements suggest that the room-temperature emissions of the complexes are due to thermally activated delayed fluorescence from the metal-to-ligand charge transfer excited state. Interestingly, by exposing the solid sample of THF-bound 1 to 4Mepy vapor, the emission intensity drastically increased and the emission color changed from blue to blue-green. Powder X-ray diffraction measurements revealed that the emission change of 1 is due to the vapor-induced ligand exchange of THF for 4Mepy, forming the strongly emissive complex 2. Further emission tuning was achieved by exposing 1 to pyrimidine or pyrazine vapors, forming green (λem = 510 nm) or orange (λem = 618 nm) emissive complexes, respectively. These results suggest that the vapor-induced ligand exchange is a promising method to control the emission color of luminescent Cu(I) complexes.