Electronic structure and photochemical reaction intermediates of octakis(1,1,2-trimethylpropyl)octasilacubane
Electronic structure and photochemical reaction intermediates of octakis(1,1,2-trimethylpropyl)octasilacubane
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DOI：
10.1016/s0009-2614(00)00357-2
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发表时间：
2000-05-12
影响因子：
2.8
通讯作者：
Hiratsuka, H
中科院分区：
文献类型：
--
作者：
Horiuchi, H;Nakano, Y;Hiratsuka, H
通过紫外-可见光谱和瞬态吸收光谱的分析，研究了八（1，1，2-三甲基丙基）八硅立方烷的电子光谱和光化学反应中间体。通过参考INDO/S-CI计算得到的结果，将UV-VIS光谱的前三个吸收带指定为从HOMO（t（1u）对称性）到LUMO（a（2u））、从HOMO-1（t（1g））到LUMO和从HOMO到LUMO + 1（t（2g））的跃迁。光化学反应中间体被确定为同分异构体，其衰变速率常数为57 ± 3 s（-1）。同分异构体被氧猝灭的速率常数为ca。3 x 10（5）M-1 s（-1）。(C)2000 Elsevier Science B. V.保留所有权利。
The electronic spectrum and photochemical reaction intermediates of octakis(1,1,2-trimethylpropyl)octasilacubane have been studied by analyzing the UV-VIS spectrum and transient absorption spectra. The first three absorption bands of the UV-VIS spectrum have been assigned to the transitions from HOMO (t(1u) symmetry) to LUMO (a(2u)), from HOMO-1 (t(1g)) to LUMO, and from HOMO to LUMO + 1 (t(2g)) by making reference to the results obtained by INDO/S-CI calculations. The photochemical reaction intermediate has been elucidated to be the isomer whose decay rate constant is 57 +/- 3 s(-1). The quenching rate constant of the isomer by oxygen is ca. 3 x 10(5) M-1 s(-1). (C) 2000 Elsevier Science B.V. All rights reserved.