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用二阶微扰方法和单组态相互作用方法分别计算了双核Au配合物Au2(SNHCH)2(a),Au2(SN2C4H3)2(b)和Au2(SN2C2H-C6H4)2(c)基态的几何结构,并在此基础上用含时密度泛函方法计算了它们的光谱。a,b,c所具有的芳香结构是逐渐增加的。计算结果表明:芳香结构的增加会加强Au之间的相互作用;在磷光发光过程中,各金属配合物都具有C(p)/芳香环(p)→S(p)跃迁属性(LLCT)、Au(p)→Au(d)电荷转移(MCCT)属性、C(p)/芳香环(p)→Au(d)跃迁属性(LMCT)和芳香环内部p电子跃迁属性(LLCT),但随着a、b、c所具有的芳香结构的增加,Au(p)→Au(d)的电荷转移(MCCT)逐渐减弱,C(p)/芳香环(p)→Au(d)的跃迁(LMCT)也逐渐减弱,芳香环内部p电子跃迁(LLCT)属性逐渐增强,即芳香结构会改变双核Au配合物的发光性质。
The ground states of binuclear Au complexes Au2 (SNHCH) 2 (a), Au2 (SN2C4H3) 2 (b) and Au2 (SN2C2H-C6H4) 2 (c) were calculated by the second-order perturbation method and single- Geometry, and on the basis of which time-dependent density functional methods have been used to calculate their spectra. a, b, c have aroma structure is gradually increased. The results show that the increase of aromatic structure enhances the interaction of Au. In the phosphorescence process, the metal complexes have the property of LLC (C (p) / aromatic ring (p) → S (p) C (p) / aromatic ring (p) → Au (d) transition property (LMCT) and the intra-aromatic p electron transition property (LLCT) of Au (p) → Au The charge transfer (MCCT) of Au (p) → Au (d) gradually decreases and the transition of C (p) / aromatic ring (p) → Au (d) LMCT) also gradually weakened, and the property of p-electron transition (LLCT) in the aromatic ring gradually increased. That is, the aromatic structure changes the luminescent properties of the binuclear Au complex.