The AuI complex [Au(Ph2PCH2py)2]BF4 (1) was prepared by mixing (tetrahydrothiophene)gold(I) chloride with 2-[(diphenylphosphino)methyl]pyridine (Ph2PCH2py) in dichloromethane. The addition of [Cu(NCCH3)4]BF4 to 1 produced green-luminescent [AuCu(Ph2PCH2py)2(NCCH3)2](BF4)2 (2). When crystals of 2 were exposed to air, two acetonitrile molecules were lost to form crystals of yellow-luminescent [AuCu(Ph2PCH2py)2](BF4)2 (3). This simple solvent loss perturbs the environment around the CuI center, and the Au···Cu distance shortens from 3.3 to 2.8 A. Crystallization of 2 or 3 from dichloromethane produced the two-coordinate CuI–solvate complex, [AuCu(Ph2PCH2py)2](BF4)2·CH2Cl2 (3·CH2Cl2). Compound 3 exhibits temperature-dependent emissions from 77 to 298 K (543 nm), 298 to 343 K (551 nm), and above 343 K (505 nm) that is reversed upon return to room temperature. The low-temperature emission is typical of complexes with luminescent rigidochromic properties. However, based on differential scanning calorimetry, a phase change is responsible for the high-temperature emission of 3.

中文翻译：

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金（I）-铜（I）膦-吡啶络合物中的发光热致变色

AuI复合物[Au(Ph2PCH2py)2]BF4(1)是通过在二氯甲烷中混合(四氢噻吩)金(I)与2-[(二苯基膦)甲基]吡啶(Ph2PCH2py)来制备的。将 [Cu(NCCH3)4]BF4 添加到 1 中产生绿色发光的 [AuCu(Ph2PCH2py)2(NCCH3)2](BF4)2 (2)。当2的晶体暴露在空气中时，失去两个乙腈分子，形成黄色发光的晶体[AuCu(Ph2PCH2py)2](BF4)2 (3)。这种简单的溶剂损失扰乱了 CuI 中心周围的环境，Au···Cu 距离从 3.3 A 缩短到 2.8 A。从二氯甲烷中结晶 2 或 3 产生了双配位的 CuI-溶剂化物络合物，[AuCu(Ph2PCH2py)2 ](BF4)2·CH2Cl2 (3·CH2Cl2)。化合物 3 在 77 至 298 K (543 nm)、298 至 343 K (551 nm)、和高于 343 K (505 nm)，返回室温后会发生逆转。低温发射是具有发光刚性变色特性的复合物的典型特征。然而，基于差示扫描量热法，相变是 3 的高温发射的原因。