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Issue 42, 2016
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Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand

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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.

Graphical abstract: Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand

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Publication details

The article was received on 05 May 2016, accepted on 09 Jun 2016 and first published on 09 Jun 2016


Article type: Paper
DOI: 10.1039/C6DT01756H
Citation: Dalton Trans., 2016,45, 16575-16584
  • Open access: Creative Commons BY-NC license
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    Chiral heterobimetallic chains from a dicyanideferrite building block including a π-conjugated TTF annulated ligand

    L. Cui, Z. Lv, C. F. Leong, J. Ru, D. M. D'Alessandro, Y. Song and J. Zuo, Dalton Trans., 2016, 45, 16575
    DOI: 10.1039/C6DT01756H

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