Salts of ammonium-crown ether supramolecular cation with bis(maleonitriledithiolato)copperate(II): Crystal structures, magnetic susceptibilities, single crystal EPR spectra and DFT calculation

• Published in: Inorganica Chimica Acta Vol. 358; no. 13; pp. 3841 - 3848
• Main Authors: Wen, Lili, Sui, Yunxia, Ren, Xiaoming, Ni, Zhaoping, Dang, Dongbin, Li, Yizhi, Meng, Qingjin, Gao, Song
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.09.2005
• Subjects: Bis(maleonitriledithiolato)copperate; Crown ether; DFT calculation; H-bonding interaction; Single crystal EPR; Supramolecular cation; H-bonding interaction; Crown ether; Single crystal EPR; DFT calculation; Bis(maleonitriledithiolato)copperate; Supramolecular cation
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.06.030

The crystal structures, magnetic susceptibilities and single-crystal X-band EPR studies on two salts consisting of ammonium-crown ether supramolecular cation with bis(maleonitriledithiolato)copperate (II), (NH 4) 2(15-crown-5) 3[Cu(mnt) 2] ( 1) and (NH 4) 2(benzo-15-crown-5) 4[Cu(mnt) 2] · 0.5H 2O ( 2) have been reported. The spin-density distribution in the anionic moiety of 2 are calculated by DFT method and compared with the experimental data. Two salts consisting of ammonium-crown ether supramolecular cation with bis(maleonitriledithiolato)copperate (II), (NH 4) 2(15-crown-5) 3[Cu(mnt) 2] ( 1) and (NH 4) 2(benzo-15-crown-5) 4[Cu(mnt) 2] · 0.5H 2O ( 2), have been synthesized and structurally characterized. The distinct structures of supramolecular cation, an unusual triple-decker dication in 1 and a sandwich dimer in 2, were observed. X-band EPR studies on the single crystals of both 1 and 2 have been carried out at room temperature, which revealed that 1 possesses a single resonance line whereas 2 shows a perfect hyperfine structure. The spin-density distribution in the anionic moiety of 2 is calculated on DFT method and compared well with the experimental data.