期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 8, 页码 3040-3051出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b13510
关键词
-
资金
- National Science Foundation (NSF) [DMR-1611525]
- Nanoporous Materials Genome Center of the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences [DE-FG02-17ER16362]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- NSF
- Division Of Materials Research [1611525] Funding Source: National Science Foundation
The isostructural, two-dimensional metal-organic frameworks (H2NMe2)(2)M-2(Cl(2)dhbq)(3) (M = Ti, V; Cl(2)dhbq(n-) = deprotonated 2,5-dichloro-3,6-dihydroxybenzoquinone) and (H2NMe2)(1.5)Cr-2(dhbq)(3) (dhbq(n-) = deprotonated 2,5-dihydroxybenzoquinone) are synthesized and investigated by spectroscopic, magnetic, and electrochemical methods. The three frameworks exhibit substantial differences in their electronic structures, and the bulk electronic conductivities of these phases correlate with the extent of delocalization observed via UV-vis-NIR and IR spectroscopies. Notably, substantial metal-ligand covalency in the vanadium phase results in the quenching of ligand-based spins, the observation of simultaneous metal- and ligand-based redox processes, and a high electronic conductivity of 0.45 S/cm. A molecular orbital analysis of these materials and a previously reported iron congener suggests that the differences in conductivity can be explained by correlating the metal-ligand energy alignment with the energy of intervalence charge-transfer transitions, which should determine the barrier to charge hopping in the mixed-valence frameworks.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据