Photophysical properties changes caused by hypercoordination of organosilicon compounds: From trianthrylfluorosilane to trianthryldifluorosilicate
Photophysical properties changes caused by hypercoordination of organosilicon compounds: From trianthrylfluorosilane to trianthryldifluorosilicate
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DOI：
10.1021/ja001042q
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发表时间：
2000-07-19
影响因子：
15
通讯作者：
Tamao, K
中科院分区：
文献类型：
--
作者：
Yamaguchi, S;Akiyama, S;Tamao, K
Modification of π-electron systems by the main group elements represents a new direction toward the construction of organic materials with unusual electronic structures and with unique functions such as sensory materials. One promising way is the use of specific orbital interactions between carbon π-conjugated systems and the main-group element moieties. 1 Another potential way may be to take advantage of the hypercoordination abilities of the main-group elements. The latter involves the electronic and structural perturbations induced by hypercoordination. For example, in the case of the group 14 compounds having extended π-electron systems as substituents, the structural change from tetrahedral to trigonal bipyramidal by pentacoordination would cause a change in the interligand through-space interaction, as visualized in Figure 1. This perturbation by the structural change in addition to the intrinsic electronic perturbation by the hypercoordination would substantially change the properties of the π-systems. However, little attention has been paid to this possibility so far, 2 despite extensive studies on the hypercoordinate main-group element compounds from the viewpoints of their syntheses, structures and reactivities. 3 In this contribution, we present the first example of controlling the photophysical properties derived from the hypercoordination of group 14 elements. As a group 14 compound having extended π-conjugated substituents, tri (9-anthryl) fluorosilane 14 was used in this study. In comparison with anthracene itself (λabs, 0-0 376 nm, λem, 0-0 381 nm, Φf 0.31 in THF), compound 1 has red-shifted absorption and emission maxima and a significantly lower quantum yield (λabs, 0-0 401 nm, λem, 0-0 416 nm, Φf 0.033 in THF). 4 These unique photophysical properties, due to the through-space interaction between the anthryl groups, render it a suitable material for the present study.
