Dipolar NLO Chromophores Bearing Diazine Rings as pi-Conjugated Linkers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F17%3A39910731" target="_blank" >RIV/00216275:25310/17:39910731 - isvavai.cz</a>

Výsledek na webu

<a href="http://pubs.acs.org/doi/ipdf/10.1021/acs.joc.7b01442" target="_blank" >http://pubs.acs.org/doi/ipdf/10.1021/acs.joc.7b01442</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.7b01442" target="_blank" >10.1021/acs.joc.7b01442</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Dipolar NLO Chromophores Bearing Diazine Rings as pi-Conjugated Linkers

Popis výsledku v původním jazyce

The synthesis of a series of push pull derivatives bearing triphenylamine electron-donating group, cyclopenta[c]thiophen4,6-dione electron acceptor and various pi-linkers including (hetero)aromatic fragments is reported. All target chromophores with systematically varied pi-linker structure were further investigated by electrochemistry, absorption measurements, and EFISH experiments in conjunction with DFT calculations. Based on electrochemical and photophysical measurements, when a polarizable 2,5-thienylene moiety is embedded into the chromophore pi-backbone the highest intramolecular charge transfer (ICT) is observed. Benzene, pyrimidine, and pyridazine derivatives exhibit lower polarizability and extent of the ICT across these pi-linkers. The elongation of the pi-conjugated system via additional ethenylene linker results in a significant reduction of the HOMO-LUMO gap and an enhancement of the NLO response. Whereas it does not significantly influence electrochemical and linear optical properties, the orientation of the pyrimidine ring seems to be a key parameter on the mu beta value due to significant variation of the dipolar moment (mu) value. In 2a and 2c, pyrimidine is oriented to behave as an acceptor and thus generate dipolar molecule with pc above 5 D, whereas in 2b and 2d ground state dipole moment is significantly reduced. This study seems to indicate a high aromaticity of pyrimidine and pyridazine derivatives, close to the benzene analogues and significantly higher than thiophene analogues.

Název v anglickém jazyce

Dipolar NLO Chromophores Bearing Diazine Rings as pi-Conjugated Linkers

Popis výsledku anglicky

The synthesis of a series of push pull derivatives bearing triphenylamine electron-donating group, cyclopenta[c]thiophen4,6-dione electron acceptor and various pi-linkers including (hetero)aromatic fragments is reported. All target chromophores with systematically varied pi-linker structure were further investigated by electrochemistry, absorption measurements, and EFISH experiments in conjunction with DFT calculations. Based on electrochemical and photophysical measurements, when a polarizable 2,5-thienylene moiety is embedded into the chromophore pi-backbone the highest intramolecular charge transfer (ICT) is observed. Benzene, pyrimidine, and pyridazine derivatives exhibit lower polarizability and extent of the ICT across these pi-linkers. The elongation of the pi-conjugated system via additional ethenylene linker results in a significant reduction of the HOMO-LUMO gap and an enhancement of the NLO response. Whereas it does not significantly influence electrochemical and linear optical properties, the orientation of the pyrimidine ring seems to be a key parameter on the mu beta value due to significant variation of the dipolar moment (mu) value. In 2a and 2c, pyrimidine is oriented to behave as an acceptor and thus generate dipolar molecule with pc above 5 D, whereas in 2b and 2d ground state dipole moment is significantly reduced. This study seems to indicate a high aromaticity of pyrimidine and pyridazine derivatives, close to the benzene analogues and significantly higher than thiophene analogues.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

—

Svazek periodika

82

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

17

Strana od-do

9435-9451

Kód UT WoS článku

000411304500019

EID výsledku v databázi Scopus

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