Vaddamanu Moulali, Sathyanarayana Arruri, Masaya Yamane, Sugiyama Shohei, Kazuhisa Ozaki, Velappan Kavitha, Nandeshwar Muneshwar, Hisano Kyohei, Tsutsumi Osamu, Prabusankar Ganesan
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, TS, 502285, India.
Department of Applied Chemistry, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, 525-8577, Japan.
Chem Asian J. 2021 Mar 1;16(5):521-529. doi: 10.1002/asia.202001380. Epub 2021 Feb 1.
The synthesis and the luminescence features of three gold(I)-N-heterocyclic carbene (NHC) complexes are presented to study how the n-alkyl group can influence the luminescence properties in the crystalline state. The mononuclear gold(I)-NHC complexes, [(L )Au(Cl)] (1), [(L )Au(Cl)] (2), and [(L )Au(Cl)] (3) were isolated from the reactions between [(tht)AuCl] and corresponding NHC ligand precursors, [N-(9-acridinyl)-N'-(n-butyl)-imidazolium chloride, (L .HCl)], [N-(9-acridinyl)-N'-(n-pentyl)-imidazolium chloride, (L .HCl)] and [N-(9-acridinyl)-N'-(n-hexyl)-imidazolium chloride, (L .HCl)]. Their single-crystal X-ray analysis reveals the influence of the n-alkyl groups on solid-state packing. A comparison of the luminescence features of 1-3 with n-alkyl substituents is explored. The molecules 1-3 depicted blue emission in the solution state, while the yellow emission (for 1), greenish-yellow emission (for 2), and blue emission (for 3) in the crystalline phase. This paradigm emission shift arises from n-butyl to n-pentyl and n-hexyl in the crystalline state due to the carbon-carbon rotation of the n-alkyl group, which tends to promote unusual solid packing. Hence n-alkyl group adds a novel emission property in the crystalline state. Density Functional Theory and Time-Dependent Density Functional Theory calculations were carried out for monomeric complex, N-(9-acridinyl)-N'-(n-heptyl)imidazole-2-ylidene gold(I) chloride and dimeric complex, N-(9-acridinyl)-N'-(n-heptyl)imidazole-2-ylidene gold(I) chloride to understand the structural and electronic properties.
本文介绍了三种金（I）-N-杂环卡宾（NHC）配合物的合成及发光特性，以研究正烷基如何影响其晶体状态下的发光性质。单核金（I）-NHC配合物[(L )Au(Cl)] (1)、[(L )Au(Cl)] (2)和[(L )Au(Cl)] (3)是由[(tht)AuCl]与相应的NHC配体前体[N-(9-吖啶基)-N'-(正丁基)-咪唑鎓氯化物，(L .HCl)]、[N-(9-吖啶基)-N'-(正戊基)-咪唑鎓氯化物，(L .HCl)]和[N-(9-吖啶基)-N'-(正己基)-咪唑鎓氯化物，(L .HCl)]反应分离得到的。它们的单晶X射线分析揭示了正烷基对固态堆积的影响。同时探讨了具有正烷基取代基的1-3的发光特性比较。分子1-3在溶液状态下呈现蓝色发射，而在晶相中分别为黄色发射（对于1）、绿黄色发射（对于2）和蓝色发射（对于3）。这种典型的发射位移在晶体状态下从正丁基到正戊基和正己基出现，这是由于正烷基的碳-碳旋转，其倾向于促进不寻常的固体堆积。因此，正烷基在晶体状态下赋予了一种新的发射特性。对单体配合物N-(9-吖啶基)-N'-(正庚基)咪唑-2-亚基氯化金（I）和二聚体配合物N-(9-吖啶基)-N'-(正庚基)咪唑-2-亚基氯化金（I）进行了密度泛函理论和含时密度泛函理论计算，以了解其结构和电子性质。
