Institute of Inorganic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.
Inorg Chem. 2011 Jun 20;50(12):5430-41. doi: 10.1021/ic102216v. Epub 2011 May 23.
A series of novel luminescent neutral cyclometalated gold(III) complexes of the type cis-[(N^C)Au(C≡CR)(2)] (R = aryl, silyl groups) having different cyclometalating cores (N^C) have been synthesized by CuI promoted halide to alkynyl metathesis with NEt(3) as in situ deprotonating agent. Along with spectroscopic characterizations (nuclear magnetic resonance and infrared spectroscopies and electrospray ionization mass spectrometry) and elemental analysis, the molecular structures of some of the complexes have been established by single-crystal X-ray diffraction studies. Photophysical studies reveal that the complexes exhibit room-temperature phosphorescence (RTP). Experimental observations and density functional theory calculations qualitatively suggest limited participation of the metal and alkynyl ligands in the lowest energy emitting state. The nature of the emission is mainly governed by metal-perturbed (3)IL(π-π*) transitions originating from the cyclometalate part of the molecule, and its variation readily leads to the tuning of the emission wavelengths. Cyclic voltammetry measurements of selected complexes showed irreversible redox behavior with near-equivalent cathodic peak potential (E(p,c)) assigned to the C^N core.
一系列新型的中性发光的环金属化金(III)配合物 cis-[(N^C)Au(C≡CR)(2)]（R = 芳基，硅基），具有不同的环金属化核（N^C），通过 CuI 促进卤化物与炔基的交叉偶联反应，以 NEt(3)作为原位脱质子试剂合成。通过核磁共振、红外光谱和电喷雾电离质谱等光谱学特征，并结合元素分析，通过单晶 X 射线衍射研究确定了一些配合物的分子结构。光物理研究表明，这些配合物具有室温磷光（RTP）。实验观察和密度泛函理论计算定性表明，金属和炔基配体在最低能量发射态中的参与是有限的。发射的性质主要由金属干扰的（3）IL(π-π*)跃迁决定，该跃迁源于分子的环金属部分，其变化很容易导致发射波长的调谐。对选定配合物的循环伏安法测量显示出不可逆的氧化还原行为，具有近等效的阴极峰电位（E(p,c)），归因于 C^N 核。
