title: Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand.
abstract: The π-conjugated tetrathiafulvalene (TTF) annulated ligand was introduced into a dicyanometallate for the first time, leading to the synthesis of the versatile redox-active dicyanideferrite building block [(n-Bu)4N][Fe(TTFbp)(CN)2] (H2TTFbp = N-(2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-5-(picolinamido) benzo[d][1,3]dithiol-6-yl) picol inamide). The incorporation of the new precursor with chiral MnIIISchiff-base complexes resulted in two enantiopure one-dimensional complexes, [Mn((R,R)-salphen)Fe(TTFbp)(CN)2]n(2-(RR)) and [Mn((S,S)-salphen)Fe(TTFbp)(CN)2]n(2-(SS)) (Salphen = N,N'-1,2-diphenylethylene-bis(salicylideneiminato) dianion), which were synthesized and structurally characterized. Circular dichroism (CD) and vibrational circular dichroism (VCD) spectra confirmed the enantiomeric nature of the optically active complexes, and structural analyses revealed the formation of neutral cyanide-bridged double chains in 2-(RR) and 2-(SS). Solution and solid state CV studies revealed the redox-active characteristics of the complexes. Antiferromagnetic couplings were detected between FeIIIand MnIIIcenters within a chain, and a field-induced magnetic phase transition was observed (TN= 4.8 K). The introduction of electroactivity and chirality into cyanide-bridged complexes with interesting magnetic properties leads the way towards new multifunctional materials.
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China. zuojl@nju.edu.cn.
authors.forename: Long
authors.initials: L
authors.lastname: Cui
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China. zuojl@nju.edu.cn.
authors.forename: Zhong-Peng
authors.initials: ZP
authors.lastname: Lv
authors.affiliation: School of Chemistry, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Chanel F
authors.initials: CF
authors.lastname: Leong
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China. zuojl@nju.edu.cn.
authors.forename: Jing
authors.initials: J
authors.lastname: Ru
authors.affiliation: School of Chemistry, The University of Sydney, New South Wales 2006, Australia.
authors.forename: Deanna M
authors.initials: DM
authors.lastname: D'Alessandro
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China. zuojl@nju.edu.cn.
authors.forename: You
authors.initials: Y
authors.lastname: Song
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China. zuojl@nju.edu.cn.
authors.forename: Jing-Lin
authors.initials: JL
authors.lastname: Zuo