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Soyoung Jeon,Yuri Jeong,Le Ngoc Tram Anh,Jeyun Ju,Daeheum Cho,Yoon Jung Jang,Ryuya Tokunaga,Shinya Hayami,Kil Sik Min 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.128 No.-
In this work, we report novel enantiopure mononuclear complexes (teaH)[Ln((S,S)-dnsalcd)2] and (teaH)[Ln((R,R)-dnsalcd)2] (Ln = Eu3+ for 1 and 4, Tb3+ for 2 and 5, and Sm3+ for 3 and 6), where teaH = triethylammonium and (S,S/R,R)-H2dnsalcd = (S,S/R,R)-N,N’-bis(3,5-dinitrosalicylidene)-1,2-cyclohexanediamine. Their unique structural features have been studied by single crystal diffraction and chiral and magneticproperties have been investigated by circular dichroism and susceptibility, respectively. Notably, 1and 3 were found to be isomorphous and exhibited a single intramolecular p-p interaction between two(S,S)-dnsalcd2- ligands. In contrast, 2 and 5 were found to be isomorphous and displayed two intramolecularp-p interactions between two (S,S/R,R)-dnsalcd2- ligands. Interestingly, strong Eu3+/Sm3+-basedemissions in the solid and solution states were observed by efficient antenna effects due to the p-p interactionmodes of the coordinated ligands. Furthermore, density functional theory calculations indicatedthat 1 contained a single localized benzene group in the highest occupied molecular orbital (HOMO),whereas 2 exhibited full delocalization via p-p interactions in the HOMO.