Department of Chemistry and Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou, 215123, People's Republic of China.
Dalton Trans. 2011 Oct 7;40(37):9551-6. doi: 10.1039/c1dt10860c. Epub 2011 Aug 17.
Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the Ru(phen)(3) is enhanced when the cation interacts with the Cd(4)(SPh)(10) anion. The mechanism for the enhancement of photoluminescence has been proposed.
已合成并通过单晶分析表征了具有化学式 [M(phen)(3)][Cd(4)(SPh)(10)]·Sol（M = Ru(2+)、Fe(2+) 和 Ni(2+)，Sol = MeCN 和 H(2)O）的三种阴离子-阳离子化合物 1-3。阳离子和阴离子都是众所周知的离子，但共组装化合物的性质很有趣。讨论了晶体中甚至在溶液中阳离子和阴离子之间的分子结构和电荷转移。这些化合物是同构的，在这些晶体中发现了短的离子间相互作用，例如 π···π 堆积和 C-H···π 接触。光谱和理论计算结果都表明，Ru-phen 配合物染料和 Cd-SPh 簇之间存在阴离子-阳离子电荷转移（ACCT），这对它们的光物理性质起着重要作用。当阳离子与 Cd(4)(SPh)(10)阴离子相互作用时，Ru(phen)(3)的荧光发射强度增强。提出了增强光致发光的机理。
