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Updated: Mar 19, 2026
Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand
Long Cui1, Zhong-Peng Lv1, Chanel F Leong2
1State 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.
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 MnIII Schiff-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 FeIII and MnIII centers 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.
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