Zehnder Thomas N, Blacque Olivier, Venkatesan Koushik
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
Dalton Trans. 2014 Aug 21;43(31):11959-72. doi: 10.1039/c4dt01187b.
Stable, luminescent, and cationic monocyclometalated gold(iii) monoaryl complexes of the type (ppy)Au(FMes)(L)OTf [L = 4-phenylpyridine (), quinoline (), 4-fluoroaniline (), P(OMe)3 (), PPh3 ()], bearing different ancillary ligands, synthesized starting from the precursor complex (ppy)Au(FMes)(OH2)OTf () are reported. The preliminary assignment of the structure of the complexes by various nuclear magnetic resonance spectroscopy techniques and elemental analysis has been further corroborated by single-crystal X-ray diffraction studies. The complexes exhibit room temperature phosphorescence in solution, in neat solids and in doped PMMA films. Detailed photophysical investigations of the complexes in solution, in neat solids and in PMMA films revealed the successful tuning of the emission quantum yield (ϕp) based on the electronic properties of the ancillary ligands. The catalytic photo-oxidation of benzylic amines to their corresponding imines using molecular oxygen as the oxidant was successfully achieved in the presence of the luminescent Au(iii) complexes. It is also established that the photocatalytic performance was strongly governed by the electronic properties of the ancillary ligands on the photosensitizer as well as by the steric bulk of the substrates.
报道了一类稳定、发光且带阳离子的单环金属化金（III）单芳基配合物[(ppy)Au(FMes)(L)]⁺[OTf]⁻[L = 4 - 苯基吡啶（）、喹啉（）、4 - 氟苯胺（）、P(OMe)₃（）、PPh₃（）]，它们带有不同的辅助配体，由前体配合物[(ppy)Au(FMes)(OH₂)]⁺[OTf]⁻（）合成而来。通过各种核磁共振光谱技术和元素分析对配合物结构进行的初步归属，已通过单晶X射线衍射研究得到进一步证实。这些配合物在溶液、纯固体和掺杂的聚甲基丙烯酸甲酯（PMMA）薄膜中均表现出室温磷光。对配合物在溶液、纯固体和PMMA薄膜中的详细光物理研究表明，基于辅助配体的电子性质成功调节了发射量子产率（ϕp）。在发光的金（III）配合物存在下，以分子氧为氧化剂，苄胺成功催化光氧化为相应的亚胺。还确定了光催化性能强烈受光敏剂上辅助配体的电子性质以及底物的空间位阻影响。
