Continuous Electrical Conductivity Variation in M3(Hexaiminotriphenylene)2 (M = Co, Ni, Cu) MOF Alloys

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-...

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Vydáno v:Journal of the American Chemical Society Ročník 142; číslo 28; s. 12367
Hlavní autoři: Chen, Tianyang, Dou, Jin-Hu, Yang, Luming, Sun, Chenyue, Libretto, Nicole J, Skorupskii, Grigorii, Miller, Jeffrey T, Dincă, Mircea
Médium: Journal Article
Jazyk:angličtina
Vydáno: 15.07.2020
ISSN:1520-5126, 1520-5126
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Shrnutí: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 (MxM'3-x)(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 (CoxNi3-x)(HITP)2 alloys scales inversely with an increasing Ni percentage, confirming thermally activated bulk transport.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 (MxM'3-x)(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 (CoxNi3-x)(HITP)2 alloys scales inversely with an increasing Ni percentage, confirming thermally activated bulk transport.
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ISSN:1520-5126
1520-5126
DOI:10.1021/jacs.0c04458