Glebko Nina, Dau Thuy Minh, Melnikov Alexei S, Grachova Elena V, Solovyev Igor V, Belyaev Andrey, Karttunen Antti J, Koshevoy Igor O
Department of Chemistry, University of Eastern Finland, Yliopistokatu 7, Joensuu, Finland.
Peter the Great St. Petersburg Polytechnic University, Polytechnicheskaya, 29, St. Petersburg, Russia.
Chemistry. 2018 Feb 26;24(12):3021-3029. doi: 10.1002/chem.201705544. Epub 2018 Feb 1.
A series of gold(I) iodide complexes 1-11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di- (1-7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal-metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of (X+M)-centered (X=halogen; M=metal) and XLCT (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (λ=545 nm, for 11) to near-IR (λ=698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of ππ* and (X+M)C/ XLCT nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.
一系列碘化亚金（I）配合物1 - 11已由二膦、三膦和四膦配体制备而成。晶体学研究表明，二核（1 - 7）和四核（11）化合物具有线性配位的金（I）离子，且存在短的金-金相互作用。它们的发光行为由膦性质、金属-金属相互作用以及分子间晶格定义的相互作用共同影响。所提出的以（X + M）为中心（X = 卤素；M = 金属）和XLCT（卤素到配体的电荷转移）的电子跃迁对最低激发态的可变贡献，受超分子堆积影响，可能是室温发射颜色从绿色（对于11，λ = 545 nm）变为近红外（对于2，λ = 698 nm）的原因。双核化合物6和7在冷却时表现出明显的发光热致变色，蓝移高达5750 cm⁻¹。这种发射能量的显著变化归因于存在两个ππ*和（X + M）C/XLCT性质的耦合三重激发态，其存在取决于分子结构和晶格排列。
