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Statements

Subject Item
n2:RIV%2F61388963%3A_____%2F14%3A00431050%21RIV15-AV0-61388963
rdf:type
skos:Concept n12:Vysledek
dcterms:description
Unlike p-electron chromophores, the peralkylated n-tetrasilane sigma-electron chromophore resembles a chameleon in that its electronic spectrum changes dramatically as its silicon backbone is twisted almost effortlessly from the syn to the anti conformation (changing the SiSiSiSi dihedral angle omega from 0 to 180 degrees). A combination of UV absorption, magnetic circular dichroism (MCD), and linear dichroism (LD) spectroscopy on conformationally controlled tetrasilanes 1-9, which cover fairly evenly the full range of angles omega, permitted a construction of an experimental correlation diagram for three to four lowest valence electronic states. The free chain tetrasilane n-Si4Me10(10), normally present as a mixture of three enantiomeric conformer pairs of widely different angles w, has also been included in our study. The spectral trends are interpreted in terms of avoided crossings of 1B with 2B and 2A with 3A states, in agreement with SAC-CI calculations on the excited states of 1-7 and conformers of 10. Unlike p-electron chromophores, the peralkylated n-tetrasilane sigma-electron chromophore resembles a chameleon in that its electronic spectrum changes dramatically as its silicon backbone is twisted almost effortlessly from the syn to the anti conformation (changing the SiSiSiSi dihedral angle omega from 0 to 180 degrees). A combination of UV absorption, magnetic circular dichroism (MCD), and linear dichroism (LD) spectroscopy on conformationally controlled tetrasilanes 1-9, which cover fairly evenly the full range of angles omega, permitted a construction of an experimental correlation diagram for three to four lowest valence electronic states. The free chain tetrasilane n-Si4Me10(10), normally present as a mixture of three enantiomeric conformer pairs of widely different angles w, has also been included in our study. The spectral trends are interpreted in terms of avoided crossings of 1B with 2B and 2A with 3A states, in agreement with SAC-CI calculations on the excited states of 1-7 and conformers of 10.
dcterms:title
Electronic Transitions in Conformationally Controlled Tetrasilanes with a Wide Range of SiSiSiSi Dihedral Angles Electronic Transitions in Conformationally Controlled Tetrasilanes with a Wide Range of SiSiSiSi Dihedral Angles
skos:prefLabel
Electronic Transitions in Conformationally Controlled Tetrasilanes with a Wide Range of SiSiSiSi Dihedral Angles Electronic Transitions in Conformationally Controlled Tetrasilanes with a Wide Range of SiSiSiSi Dihedral Angles
skos:notation
RIV/61388963:_____/14:00431050!RIV15-AV0-61388963
n4:aktivita
n11:I
n4:aktivity
I
n4:cisloPeriodika
30
n4:dodaniDat
n7:2015
n4:domaciTvurceVysledku
Michl, Josef
n4:druhVysledku
n13:J
n4:duvernostUdaju
n6:S
n4:entitaPredkladatele
n5:predkladatel
n4:idSjednocenehoVysledku
14220
n4:idVysledku
RIV/61388963:_____/14:00431050
n4:jazykVysledku
n15:eng
n4:klicovaSlova
conformational effects; electronic spectra; SAC-CI calculations; silicon; UV/Vis spectroscopy
n4:klicoveSlovo
n10:UV%2FVis%20spectroscopy n10:electronic%20spectra n10:conformational%20effects n10:SAC-CI%20calculations n10:silicon
n4:kodStatuVydavatele
DE - Spolková republika Německo
n4:kontrolniKodProRIV
[40C6001B3AB5]
n4:nazevZdroje
Chemistry - A European Journal
n4:obor
n16:CC
n4:pocetDomacichTvurcuVysledku
1
n4:pocetTvurcuVysledku
8
n4:rokUplatneniVysledku
n7:2014
n4:svazekPeriodika
20
n4:tvurceVysledku
Ehara, M. Tamao, K. Tsuji, H. Nakatsuji, H. Fogarty, H. A. Fukuda, R. Michl, Josef Casher, D. L.
n4:wos
000339568800040
s:issn
0947-6539
s:numberOfPages
11
n8:doi
10.1002/chem.201403495