Tuning Electrical- and Photo-Conductivity by Cation Exchange within a Redox-Active Tetrathiafulvalene-Based Metal-Organic Framework.

To activate electronic and optical functions of the redox-active metal-organic framework, (Me NH )[In (TTFTB)]⋅0.7 C H OH⋅DMF (Me NH @1, TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF ) and N,N'-dimethyl-4,4'-bipyridinium (MV ). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single-crystal to single-crystal post-synthetic transformation to TTF@1 and MV@1. Both TTF and MV enhance the electrical conductivity by a factor of 10 and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox-active TTFTB bridges and MV . The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.