School of Chemistry , University of East Anglia , Norwich , NR4 7TJ , United Kingdom.
Departamento de Química Inorgánica , Universidad de Sevilla , E- 41092 Sevilla , Spain.
Inorg Chem. 2019 Feb 4;58(3):2020-2030. doi: 10.1021/acs.inorgchem.8b02987. Epub 2019 Jan 17.
Cyclometalated gold(III) complexes of the type (C∧N∧C)AuX [HC∧N∧CH = 2,6-bis(4-BuCH)pyrazine; 2,6-bis(4-BuCH)pyridine, or 2,6-bis(4-BuCH)4-Bupyridine; X = CN, CH(COMe), or CH(CN)] have been used as building blocks for the construction of the first family of Au/Ag aggregates. The crystal structures of these aggregates reveal the formation of complex architectures in which the Ag cations are stabilized by the basic centers present on each of the Au precursors. The photophysical properties of these aggregates are reported. Compared to mononuclear pincer complexes, a general red-shift and an increase in the emission intensity are observed. In agreement with DFT calculations, the lowest energy absorption and the emission are assigned to IL(C∧N∧C) and IL(C∧N∧C) transitions dominated by the HOMO and the LUMO orbitals.
已将(C∧N∧C)AuX [HC∧N∧CH = 2,6-双(4-BuCH)吡嗪;2,6-双(4-BuCH)吡啶或 2,6-双(4-BuCH)4-Bupyridine;X = CN,CH(COMe)或 CH(CN)]类型的环金属化金(III)配合物用作构建第一组金/银聚集体的构建块。这些聚集体的晶体结构揭示了复杂结构的形成,其中Ag 阳离子由每个 Au 前体上存在的碱性中心稳定。报道了这些聚集体的光物理性质。与单核 pincer 配合物相比,观察到一般的红移和发射强度增加。与 DFT 计算一致,最低能量吸收和发射被分配给 IL(C∧N∧C)和 IL(C∧N∧C)跃迁,由 HOMO 和 LUMO 轨道主导。