Effect of backbone conformation and its defects on electronic properties and assessment of the stabilizing role of π-π interactions in aryl substituted polysilylenes studied by DFT on deca[methyl(phenyl)silylene]s

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28610%2F16%3A43874552" target="_blank" >RIV/70883521:28610/16:43874552 - isvavai.cz</a>

Výsledek na webu

<a href="https://ccj.springeropen.com/articles/10.1186/s13065-016-0173-0" target="_blank" >https://ccj.springeropen.com/articles/10.1186/s13065-016-0173-0</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1186/s13065-016-0173-0" target="_blank" >10.1186/s13065-016-0173-0</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Effect of backbone conformation and its defects on electronic properties and assessment of the stabilizing role of π-π interactions in aryl substituted polysilylenes studied by DFT on deca[methyl(phenyl)silylene]s

Popis výsledku v původním jazyce

Background: Recent efforts in the field of mesoscale effects on the structure and properties of thin polymer films call to revival interest in conformational structure and defects of a polymer backbone which has a crucial influence on electronic properties of the material. Oligo[methyl(phenyl)silylene]s (OMPSi) as exemplary molecules were studied theoretically by DFT in the form of optimal decamers and conformationally disrupted decamers (with a kink). Results: We proved that transoid backbone conformation is true energy minimum and that a kink in the backbone causes significant hypsochromic shift of the absorption maximum (π max), while backbone conformation altering from all-eclipsed to all-anti affects π max in the opposite way. π-π stacking was investigated qualitatively through optimal geometry of OMPSi and mutual position of their phenyls along the backbone and also quantitatively by an evaluation of molecular energies obtained from single point calculations with functionals, which treat the dispersion effect in the varying range of interaction. Conclusions: The kink was identified as a realistic element of the conformational structure that could be able to create a bend in a real aryl substituted polysilylene chain because it is stabilized by attractive π-π interactions between phenyl side groups. Graphical abstract.

Název v anglickém jazyce

Effect of backbone conformation and its defects on electronic properties and assessment of the stabilizing role of π-π interactions in aryl substituted polysilylenes studied by DFT on deca[methyl(phenyl)silylene]s

Popis výsledku anglicky

Background: Recent efforts in the field of mesoscale effects on the structure and properties of thin polymer films call to revival interest in conformational structure and defects of a polymer backbone which has a crucial influence on electronic properties of the material. Oligo[methyl(phenyl)silylene]s (OMPSi) as exemplary molecules were studied theoretically by DFT in the form of optimal decamers and conformationally disrupted decamers (with a kink). Results: We proved that transoid backbone conformation is true energy minimum and that a kink in the backbone causes significant hypsochromic shift of the absorption maximum (π max), while backbone conformation altering from all-eclipsed to all-anti affects π max in the opposite way. π-π stacking was investigated qualitatively through optimal geometry of OMPSi and mutual position of their phenyls along the backbone and also quantitatively by an evaluation of molecular energies obtained from single point calculations with functionals, which treat the dispersion effect in the varying range of interaction. Conclusions: The kink was identified as a realistic element of the conformational structure that could be able to create a bend in a real aryl substituted polysilylene chain because it is stabilized by attractive π-π interactions between phenyl side groups. Graphical abstract.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CE - Biochemie

OECD FORD obor

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Projekt

<a href="/cs/project/LO1504" target="_blank" >LO1504: Centrum polymerních systémů plus</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2016

Kód důvěrnosti údajů

C - Předmět řešení projektu podléhá obchodnímu tajemství (§ 504 Občanského zákoníku), ale název projektu, cíle projektu a u ukončeného nebo zastaveného projektu zhodnocení výsledku řešení projektu (údaje P03, P04, P15, P19, P29, PN8) dodané do CEP, jsou upraveny tak, aby byly zveřejnitelné.

Název periodika

Chemistry Central Journal

ISSN

1752-153X

e-ISSN

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Svazek periodika

10

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

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Kód UT WoS článku

000375639100001

EID výsledku v databázi Scopus

2-s2.0-84965076130