1997
DOI: 10.1021/ja963724c
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An Abrupt Solvatochromic Transition in a Polar Polysilane

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Cited by 45 publications
(47 citation statements)
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“…For n = 16, we also optimized the all-cisoid conformation (c; w % 378). From earlier work, [12,13,15,20] the g, o,and t conformations at internal SiSi bonds are known to represent local minima on the potentiale nergy surfaces of short permethylated oligosilanes, and chains substituted with longera lkyls occasionally show additional minima at c and d conformations. The optimization of the e, d,a nd a conformations, which do not correspond to minimai nt he potential energy surface of permethylated oligosilanes, was constrained in that the dihedral angles were set equal to the values specified above.…”
Section: Methods and Resultsmentioning
confidence: 98%
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“…For n = 16, we also optimized the all-cisoid conformation (c; w % 378). From earlier work, [12,13,15,20] the g, o,and t conformations at internal SiSi bonds are known to represent local minima on the potentiale nergy surfaces of short permethylated oligosilanes, and chains substituted with longera lkyls occasionally show additional minima at c and d conformations. The optimization of the e, d,a nd a conformations, which do not correspond to minimai nt he potential energy surface of permethylated oligosilanes, was constrained in that the dihedral angles were set equal to the values specified above.…”
Section: Methods and Resultsmentioning
confidence: 98%
“…[1][2][3][4] They are sensitive to the backbone conformation and as ar esult lead to phenomena such as thermochromism, [5][6][7][8][9] piezochromism, [10,11] electrochromism, [12] ionochromism, [13,14] and solvatochromism. [15] Also their single-molecule electrical conductivity appearst od epend on conformation. [16] In long polysilane chains, conformational segmentation into individual chromophores is important for optical absorption, emission, and charge-transport properties.…”
Section: Introductionmentioning
confidence: 99%
“…[1] Their intense electronic absorption in the near UV was found to be sensitive to the electronic nature of the substituents and the conformation of the silicon backbone, as reflected in the thermochromism, [2] solvatochromism, [3] and ionochromism [4] of some oligosilanes. Recent studies on linear derivatives with discrete conformations have shown that sconjugation is more effective in an anti-conformation (Si-SiSi-Si dihedral angle w = 1808) than in conformations with small dihedral angles, such as syn, cisoid, or even gauche (w = 0-608).…”
mentioning
confidence: 99%
“…The electronic absorption and emission spectra of these compounds are very sensitive to chain conformation, as manifested in the thermochromism (15,16), piezochromism (17), solvatochromism (18), and related properties (19,20) of polysilanes. They therefore represent an especially suitable vehicle for the study of the incompletely understood but clearly important phenomenon of -electron delocalization and particularly of its structural and conformational dependence.…”
mentioning
confidence: 99%