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

被引:266
作者
Chen, Tianyang [1 ]
Dou, Jin-Hu [1 ]
Yang, Luming [1 ]
Sun, Chenyue [1 ]
Libretto, Nicole J. [2 ]
Skorupskii, Grigorii [1 ]
Miller, Jeffrey T. [2 ]
Dinca, Mircea [1 ]
机构
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
[2] Purdue Univ, Davidson Sch Chem Engn, W Lafayette, IN 47907 USA
基金
美国国家科学基金会;
关键词
X-RAY PHOTOELECTRON; METAL-ORGANIC FRAMEWORK; ABSORPTION-EDGE; SPECTROSCOPY; COMPLEXES; EPR; NICKEL;
D O I
10.1021/jacs.0c04458
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 M-3(HITP)(2) (M = Co, Ni, Cu; HITP = 2,3,6,7,10,11-hexaiminotriphenylene). The isostructurality in the M-3(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.
引用
收藏
页码:12367 / 12373
页数:7
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