Carbazole/fluorene-substituted 5-phenyl-2,2′-bipyridine D–π–A fluorophores: photophysical data, hyperpolarizability and CT-indices

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Carbazole/fluorene-substituted 5-phenyl-2,2′-bipyridine D–π–A fluorophores: photophysical data, hyperpolarizability and CT-indices. / Starnovskaya, Ekaterina S.; Valieva, Maria I.; Aluru, Rammohan et al.
In: New Journal of Chemistry, Vol. 47, No. 26, 2023, p. 12393-12402.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{9f2a4d3723f646b6965ffc3e6bcc5ea1,

title = "Carbazole/fluorene-substituted 5-phenyl-2,2′-bipyridine D–π–A fluorophores: photophysical data, hyperpolarizability and CT-indices",

abstract = "Push-pull fluorophores exhibiting pronounced intramolecular charge transfer have a low fluorescence quantum yield. Here we report a new series of D-pi-A push-pull fluorophores containing a unified 2,2 '-bipyridine domain acceptor with terminal electron-donating carbazole/fluorene groups that exhibit good fluorescence performance. All fluorophores demonstrated high fluorescence quantum yields of up to 0.99 and large Stokes shifts of up to 10 394 cm(-1) (157 nm). For the first time, the solvatochromic method was successfully applied to 2,2 '-bipyridine compounds of this type to evaluate their static and dynamic hyperpolarizability coefficients. Due to their remarkable fluorescence capability, two-photon emission cross sections were measured for three dyes using the two-photon fluorescence method. Both experimental studies and calculated charge transfer indices (CT-indices) confirmed the greatest charge separation in carbazole-substituted isomers. The annelation of the cyclopentene moiety to the 2,2 '-bipyridine core inhibited the formation of aggregates in the solid state and significantly increased the energy gap. Finally, a planarized ICT (PLICT) process was confirmed for fluorene-containing fluorophores based on theoretical calculations in the ground and excited states in various solvents. The synthesized carbazole-containing 2,2 '-bipyridines are very promising ligands for constructing metallic NLO-phores, while fluorene-based fluorophores with a predominant PLICT state can be considered as promising environment polarity sensitive fluorescent dyes and biological probes to detect structural changes in proteins/biomolecular interactions and optical switches.",

author = "Starnovskaya, {Ekaterina S.} and Valieva, {Maria I.} and Rammohan Aluru and Kopchuk, {Dmitry S.} and Khasanov, {Albert F.} and Taniya, {Olga S.} and Novikov, {Alexander S.} and Kalinichev, {Alexey A.} and Sougata Santra and Zyryanov, {Grigory V.} and Ranu, {Brindban C.}",

note = "This work was supported by the by the RUDN University Strategic Academic Leadership Program (quantum chemical calculations), Russian Science Foundation Grant # 19-73-10144P (photophysical studies), and by the Ministry of Science and Higher Education of the Russian Federation, Ref. # 075-15-2022-1118 dated 29 June 2022 (synthesis of 5-phenyl-2,2′-bipyridines).",

year = "2023",

doi = "10.1039/D3NJ00394A",

language = "English",

volume = "47",

pages = "12393--12402",

journal = "New Journal of Chemistry",

issn = "1144-0546",

publisher = "Royal Society of Chemistry",

number = "26",

}

RIS

TY - JOUR

T1 - Carbazole/fluorene-substituted 5-phenyl-2,2′-bipyridine D–π–A fluorophores: photophysical data, hyperpolarizability and CT-indices

AU - Starnovskaya, Ekaterina S.

AU - Valieva, Maria I.

AU - Aluru, Rammohan

AU - Kopchuk, Dmitry S.

AU - Khasanov, Albert F.

AU - Taniya, Olga S.

AU - Novikov, Alexander S.

AU - Kalinichev, Alexey A.

AU - Santra, Sougata

AU - Zyryanov, Grigory V.

AU - Ranu, Brindban C.

N1 - This work was supported by the by the RUDN University Strategic Academic Leadership Program (quantum chemical calculations), Russian Science Foundation Grant # 19-73-10144P (photophysical studies), and by the Ministry of Science and Higher Education of the Russian Federation, Ref. # 075-15-2022-1118 dated 29 June 2022 (synthesis of 5-phenyl-2,2′-bipyridines).

PY - 2023

Y1 - 2023

N2 - Push-pull fluorophores exhibiting pronounced intramolecular charge transfer have a low fluorescence quantum yield. Here we report a new series of D-pi-A push-pull fluorophores containing a unified 2,2 '-bipyridine domain acceptor with terminal electron-donating carbazole/fluorene groups that exhibit good fluorescence performance. All fluorophores demonstrated high fluorescence quantum yields of up to 0.99 and large Stokes shifts of up to 10 394 cm(-1) (157 nm). For the first time, the solvatochromic method was successfully applied to 2,2 '-bipyridine compounds of this type to evaluate their static and dynamic hyperpolarizability coefficients. Due to their remarkable fluorescence capability, two-photon emission cross sections were measured for three dyes using the two-photon fluorescence method. Both experimental studies and calculated charge transfer indices (CT-indices) confirmed the greatest charge separation in carbazole-substituted isomers. The annelation of the cyclopentene moiety to the 2,2 '-bipyridine core inhibited the formation of aggregates in the solid state and significantly increased the energy gap. Finally, a planarized ICT (PLICT) process was confirmed for fluorene-containing fluorophores based on theoretical calculations in the ground and excited states in various solvents. The synthesized carbazole-containing 2,2 '-bipyridines are very promising ligands for constructing metallic NLO-phores, while fluorene-based fluorophores with a predominant PLICT state can be considered as promising environment polarity sensitive fluorescent dyes and biological probes to detect structural changes in proteins/biomolecular interactions and optical switches.

AB - Push-pull fluorophores exhibiting pronounced intramolecular charge transfer have a low fluorescence quantum yield. Here we report a new series of D-pi-A push-pull fluorophores containing a unified 2,2 '-bipyridine domain acceptor with terminal electron-donating carbazole/fluorene groups that exhibit good fluorescence performance. All fluorophores demonstrated high fluorescence quantum yields of up to 0.99 and large Stokes shifts of up to 10 394 cm(-1) (157 nm). For the first time, the solvatochromic method was successfully applied to 2,2 '-bipyridine compounds of this type to evaluate their static and dynamic hyperpolarizability coefficients. Due to their remarkable fluorescence capability, two-photon emission cross sections were measured for three dyes using the two-photon fluorescence method. Both experimental studies and calculated charge transfer indices (CT-indices) confirmed the greatest charge separation in carbazole-substituted isomers. The annelation of the cyclopentene moiety to the 2,2 '-bipyridine core inhibited the formation of aggregates in the solid state and significantly increased the energy gap. Finally, a planarized ICT (PLICT) process was confirmed for fluorene-containing fluorophores based on theoretical calculations in the ground and excited states in various solvents. The synthesized carbazole-containing 2,2 '-bipyridines are very promising ligands for constructing metallic NLO-phores, while fluorene-based fluorophores with a predominant PLICT state can be considered as promising environment polarity sensitive fluorescent dyes and biological probes to detect structural changes in proteins/biomolecular interactions and optical switches.

UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001008996400001

UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85163946975

U2 - 10.1039/D3NJ00394A

DO - 10.1039/D3NJ00394A

M3 - Article

VL - 47

SP - 12393

EP - 12402

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 26

ER -

ID: 41602003