Intrinsic Semiconducting Behavior in a Large Mixed-Valent Uranium(V/VI) Cluster

被引：54

作者：

Zhang, Mingxing ^{[1
,2
,3
,4
]}

Liang, Chengyu ^{[1
,2
]}

Cheng, Guo-Dong ^{[5
]}

Chen, Junchang ^{[1
,2
]}

Wang, Yumin ^{[1
,2
]}

He, Linwei ^{[1
,2
]}

Cheng, Liwei ^{[1
,2
]}

Gong, Shicheng ^{[1
,2
]}

Zhang, Duo ^{[1
,2
]}

Li, Jiong ^{[6
]}

Hu, Shu-Xian ^{[5
]}

Juan, Diwu ^{[1
,2
]}

Wu, Guozhong ^{[3
]}

Wang, Yaxing ^{[1
,2
]}

Chai, Zhifang ^{[1
,2
]}

Wang, Shuao ^{[1
,2
]}

机构：

[1] Soochow Univ, State Key Lab Radiat Med & Protect, Sch Radiol & Interdisciplinary Sci RAD X, Suzhou 215123, Peoples R China

[2] Soochow Univ, Jiangsu Higher Educ Inst, Collaborat Innovat Ctr Radiat Med, Suzhou 215123, Peoples R China

[3] Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201800, Peoples R China

[4] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

[5] Univ Sci & Technol Beijing, Sch Math & Phys, Beijing 100083, Peoples R China

[6] Chinese Acad Sci, Shanghai Adv Res Inst, Shanghai Synchrotron Radiat Facil, Shanghai 201210, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 18期

基金：

中国国家自然科学基金;

关键词：

mixed-valent uranium; radiation detection; semiconductors; uranium clusters; SINGLE-MOLECULE MAGNET; PENTAVALENT; REDUCTION; TEMPERATURE; PARAMETERS; DETECTORS; COMPLEXES; CHEMISTRY; OXIDE;

D O I：

10.1002/anie.202017298

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We disclose the intrinsic semiconducting properties of one of the largest mixed-valent uranium clusters, [H3O+][U-V((UO2)-O-VI)(8)(mu(3)-O)(6)(PhCOO)(2)(Py(CH2O)(2))(4)(DMF)(4)] (Ph=phenyl, Py=pyridyl, DMF=N,N-dimethylformamide) (1). Single-crystal X-ray crystallography demonstrates that U-V center is stabilized within a tetraoxo core surrounded by eight uranyl(VI) pentagonal bipyramidal centers. The oxidation states of uranium are substantiated by spectroscopic data and magnetic susceptibility measurement. Electronic spectroscopy and theory corroborate that U-V species serve as electron donors and thus facilitate 1 being a n-type semiconductor. With the largest effective atomic number among all reported radiation-detection semiconductor materials, charge transport properties and photoconductivity were investigated under X-ray excitation for 1: a large on-off ratio of 500 and considerable charge mobility lifetime product of 2.3x10(-4) cm(2) V-1, as well as a high detection sensitivity of 23.4 mu C Gy(air)(-1) cm(-2).

引用

页码：9886 / 9890

页数：5

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