Zhang Mingxing, Liang Chengyu, Cheng Guo-Dong, Chen Junchang, Wang Yumin, He Linwei, Cheng Liwei, Gong Shicheng, Zhang Duo, Li Jiong, Hu Shu-Xian, Diwu Juan, Wu Guozhong, Wang Yaxing, Chai Zhifang, Wang Shuao
State Key Laboratory of Radiation Medicine and Protection, School for Radiological and interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of, Jiangsu Higher Education Institutions, Soochow University, Suzhou, 215123, China.
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
Angew Chem Int Ed Engl. 2021 Apr 26;60(18):9886-9890. doi: 10.1002/anie.202017298. Epub 2021 Mar 18.
We disclose the intrinsic semiconducting properties of one of the largest mixed-valent uranium clusters, [H O ][U (U O ) (μ -O) (PhCOO) (Py(CH O) ) (DMF) ] (Ph=phenyl, Py=pyridyl, DMF=N,N-dimethylformamide) (1). Single-crystal X-ray crystallography demonstrates that U 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 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 cm V , as well as a high detection sensitivity of 23.4 μC Gy cm .
我们揭示了最大的混合价态铀簇之一[H₂O][U₉(UO₂)₆(μ₃ -O)₆(PhCOO)₉(Py(CH₂OH)₂)₃(DMF)₃]（Ph = 苯基，Py = 吡啶基，DMF = N,N - 二甲基甲酰胺）（1）的本征半导体性质。单晶X射线晶体学表明，U中心稳定在由八个铀酰（VI）五角双锥中心包围的四氧核内。铀的氧化态通过光谱数据和磁化率测量得到证实。电子光谱和理论证实，U物种作为电子供体，从而使1成为n型半导体。在所有报道的辐射探测半导体材料中，1具有最大的有效原子序数，我们对其在X射线激发下的电荷传输性质和光电导性进行了研究：具有500的大开关比、2.３×10⁻³ cm² V⁻¹ s⁻¹的可观电荷迁移率寿命乘积，以及23.4 μC Gy⁻¹ cm⁻²的高探测灵敏度。
