Premium
Intrinsic Semiconducting Behavior in a Large Mixed‐Valent Uranium(V/VI) Cluster
Author(s) -
Zhang Mingxing,
Liang Chengyu,
Cheng GuoDong,
Chen Junchang,
Wang Yumin,
He Linwei,
Cheng Liwei,
Gong Shicheng,
Zhang Duo,
Li Jiong,
Hu ShuXian,
Diwu Juan,
Wu Guozhong,
Wang Yaxing,
Chai Zhifang,
Wang Shuao
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202017298
Subject(s) - uranyl , uranium , cluster (spacecraft) , crystallography , actinide , atom (system on chip) , semiconductor , materials science , pentagonal bipyramidal molecular geometry , spectroscopy , chemistry , crystal structure , analytical chemistry (journal) , inorganic chemistry , physics , chromatography , optoelectronics , quantum mechanics , computer science , embedded system , metallurgy , programming language
We disclose the intrinsic semiconducting properties of one of the largest mixed‐valent uranium clusters, [H 3 O + ][U V (U VI O 2 ) 8 (μ 3 ‐O) 6 (PhCOO) 2 (Py(CH 2 O) 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 2.3×10 −4 cm 2 V −1 , as well as a high detection sensitivity of 23.4 μC Gy air −1 cm −2 .