Photo- and Electronically Switchable Spin-Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene Ligand

Hai-Ying Wang; Jing-Yuan Ge; Carol Hua; Cheng-Qi Jiao; Yue Wu; Chanel F Leong; Deanna M D'Alessandro; Tao Liu; Jing-Lin Zuo

doi:10.1002/anie.201611824

Photo- and Electronically Switchable Spin-Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene Ligand

Angew Chem Int Ed Engl. 2017 May 8;56(20):5465-5470. doi: 10.1002/anie.201611824. Epub 2017 Apr 12.

Authors

Hai-Ying Wang¹, Jing-Yuan Ge¹, Carol Hua², Cheng-Qi Jiao³, Yue Wu¹, Chanel F Leong², Deanna M D'Alessandro², Tao Liu³, Jing-Lin Zuo¹

Affiliations

¹ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China.
² School of Chemistry, The University of Sydney, Sydney, New South Wales, 2006, Australia.
³ State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Rd., 116024, Dalian, China.

PMID: 28402592
DOI: 10.1002/anie.201611824

Abstract

A major challenge is the development of multifunctional metal-organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py)₄ ) and spin-crossover Fe^II centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO). A crystal-to-crystal transformation induced by I₂ doping has also been observed and the resulting intercalated structure determined. The conductivity could be significantly enhanced (up to 3 orders of magnitude) by modulating the electronic state of the framework via oxidative doping; SCO behavior was also modified and the photo-magnetic behavior was switched off. This work provides a new strategy to tune the spin state and conductivity of framework materials through guest-induced redox-state switching.

Keywords: iodine; iron; metal-organic frameworks; spin crossover; tetrathiafulvalenes.

Publication types

Research Support, Non-U.S. Gov't