Fujisawa Kiyoshi, Saotome Mai, Ishikawa Yoko, Young David James
Department of Chemistry, Ibaraki University, Ibaraki 310-8512, Japan.
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571, Japan.
Nanomaterials (Basel). 2021 Nov 17;11(11):3101. doi: 10.3390/nano11113101.
Cyclic trinuclear complexes with group 11 metal(I) ions are fascinating and important to coordination chemistry. One of the ligands known to form these cyclic trinuclear complexes is pyrazolate, which is a bridging ligand that coordinates many transition metal ions in a Npz-M-Npz linear mode (Npz = pyrazolyl nitrogen atom). In these group 11 metal(I) ions, copper is the most abundant metal. Therefore, polynuclear copper(I) complexes are very important in this field. The cyclic trinuclear copper(I) complex (3,5-Phpz = 3,5-diphenyl-1-pyrazolate anion) was reported in 1988 as a landmark complex, but its photoluminescence properties have hitherto not been described. In this study, we report the photoluminescence and two different polymorphs of and its derivative [ (3-Me-5-Phpz = 3-metyl-5-phenyl-1-pyrazale anion). The substituents in cause smaller distortions in the solid-state structure and a red-shift in photoluminescence due to the presence of intermolecular cuprophilic interactions.
含有第11族金属（I）离子的环状三核配合物对配位化学而言既迷人又重要。已知能形成这些环状三核配合物的配体之一是吡唑酸根，它是一种桥连配体，以Npz-M-Npz线性模式（Npz = 吡唑基氮原子）配位许多过渡金属离子。在这些第11族金属（I）离子中，铜是含量最丰富的金属。因此，多核铜（I）配合物在该领域非常重要。环状三核铜（I）配合物（3,5-Phpz = 3,5-二苯基-1-吡唑酸根阴离子）于1988年作为一个具有里程碑意义的配合物被报道，但迄今为止其光致发光性质尚未被描述。在本研究中，我们报道了 及其衍生物[（3-Me-5-Phpz = 3-甲基-5-苯基-1-吡唑酸根阴离子）的光致发光和两种不同的多晶型物。 中的取代基由于分子间亲铜相互作用的存在，在固态结构中引起较小的畸变并导致光致发光红移。
