Azo‐Cyanamide Bridged Dinuclear Iron Complexes Exhibiting no Electronic Coupling but Moderate Magnetic Coupling between the two Iron Centers

Author:

Mao Zhong‐Dong12,Fu Jin‐Hui1,He Yong1,Song Ying1,Tan Bing‐Chang1,Chen Ling‐Ting1,Wu Xin‐Tao1,Sheng Tian‐Lu1ORCID

Affiliation:

1. State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Science Fuzhou Fujian 350002 P.R. China

2. College of Materials Science and Opto-Electronic Technology University of Chinese Academy of Sciences Beijing 100049 P.R. China

Abstract

AbstractTo investigate the effect of long‐distance organic ligand on electronic coupling between metallic atoms, the mononuclear and dinuclear complexes [Cp(dppe)Fe(apc)] (1), [{Cp(dppe)Fe}2(μ‐adpc)] (2), [{CpMe5(dppe)Fe}2(μ‐adpc) (3) and their oxidized complexes [Cp(dppe)Fe(apc)][PF6] (1[PF6]), [{Cp(dppe)Fe}2(μ‐adpc)][PF6] (2[PF6]2), [{CpMe5(dppe)Fe}2(μ‐adpc)][PF6]2 (3[PF6]2) (Cp=1,3‐cyclopentadiene, CpMe5=1,2,3,4,5‐pentamethylcyclopentadiene, dppe=1,2‐bis(diphenylphosphino)ethane), apc=4‐azo(phenylcyanamido)benzene and adpc2−=4,4′‐azodi(phenylcyanamido)) were synthesized and characterized by cyclic voltammetry, UV‐vis, single‐crystal X‐ray diffraction and Mössbauer spectra. Electrochemical measurements showed no electronic coupling between the two terminal Fe units, However, the investigation results of the magnetic properties of the two‐electron oxidized complexes indicate the presence of moderate antiferromagnetic coupling across 18 Å distance.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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