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Continuous Electrical Conductivity Variation in M3(Hexaiminotriphenylene)2 (M = Co, Ni, Cu) MOF Alloys
Tianyang Chen1, Jin-Hu Dou1, Luming Yang1
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Abstract:
We report on the continuous fine-scale tuning of band gaps over 0.4 eV and of the electrical conductivity of over 4 orders of magnitude in a series of highly crystalline binary alloys of two-dimensional electrically conducting metal-organic frameworks M3(HITP)2 (M = Co, Ni, Cu; HITP = 2,3,6,7,10,11-hexaiminotriphenylene). The isostructurality in the M3(HITP)2 series permits the direct synthesis of binary alloys (MM'3-)(HITP)2 (MM' = CuNi, CoNi, and CoCu) with metal compositions precisely controlled by precursor ratios. We attribute the continuous tuning of both band gaps and electrical conductivity to changes in free-carrier concentrations and to subtle differences in the interlayer displacement or spacing, both of which are defined by metal substitution. The activation energy of (CoNi3-)(HITP)2 alloys scales inversely with an increasing Ni percentage, confirming thermally activated bulk transport.
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