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The Design of Radical Stacks : Nitronyl-Nitroxide-Substituted Heteropentacenes. / Tretyakov, Evgeny; Keerthi, Ashok; Baumgarten, Martin и др.

в: ChemistryOpen, Том 6, № 5, 01.10.2017, стр. 642-652.

Результаты исследований: Научные публикации в периодических изданияхстатьяРецензирование

Harvard

Tretyakov, E, Keerthi, A, Baumgarten, M, Veber, S, Fedin, M, Gorbunov, D, Shundrina, I & Gritsan, N 2017, 'The Design of Radical Stacks: Nitronyl-Nitroxide-Substituted Heteropentacenes', ChemistryOpen, Том. 6, № 5, стр. 642-652. https://doi.org/10.1002/open.201700110

APA

Vancouver

Tretyakov E, Keerthi A, Baumgarten M, Veber S, Fedin M, Gorbunov D и др. The Design of Radical Stacks: Nitronyl-Nitroxide-Substituted Heteropentacenes. ChemistryOpen. 2017 окт. 1;6(5):642-652. doi: 10.1002/open.201700110

Author

Tretyakov, Evgeny ; Keerthi, Ashok ; Baumgarten, Martin и др. / The Design of Radical Stacks : Nitronyl-Nitroxide-Substituted Heteropentacenes. в: ChemistryOpen. 2017 ; Том 6, № 5. стр. 642-652.

BibTeX

@article{8d0a7c514f5149f1b0a935e0b7b2e8d6,
title = "The Design of Radical Stacks: Nitronyl-Nitroxide-Substituted Heteropentacenes",
abstract = "The first alkyl chain-anchored heteropentacene, dithieno[2,3-d;2′,3′-d′]benzo-[1,2-b;3,4-b′]dithiophene (DTmBDT), mono- or disubstituted with a nitronyl nitroxide group has been prepared through a cross-coupling synthetic procedure of the corresponding dibromo-derivative (Br2-DTmBDT) with a nitronyl nitroxide-2-ide gold(I) complex. The synthesized nitroxides possess high kinetic stability, which allowed us to investigate their structure and thermal, optical, electrochemical, and magnetic properties. Single-crystal X-ray diffraction of both mono- and diradicals revealed that the nitronyl nitroxide group lies almost in the same plane as the nearest side thiophene ring. Such arrangement favors formation of edge-to-edge dimers, which then form close π-stacks surrounded by interdigitating alkyl chains. Before melting, these nitronyl nitroxide radical substituted molecules undergo at least two different phase transitions (PTs): for the monoradical, PTs are reversible, accompanied by hysteresis, and occur near 13 and 83 °C; the diradical upon heating shows a reversible PT with hysteresis in the temperature range 2–11 °C and an irreversible PT near 135 °C. PTs of this type are absent in Br2-DTmBDT. Therefore, the step-by-step substitution of bromine atoms by nitronyl nitroxide groups changes the structural organization of DTmBDT and induces the emergence of PTs. This knowledge may facilitate crystal engineering of π-stacked paramagnets and related molecular spin devices.",
keywords = "density functional and ab initio calculations, EPR spectroscopy, fused thiophene, nitronyl nitroxides, π-stacking, DNA-PK, COMPLEXES, EX-SITU GENERATION, OXIDATIVE ADDITION, density functional and ab into calculations, pi-stacking, CARBON-MONOXIDE, PALLADIUM-CATALYZED CARBONYLATION, ARYL HALIDES, ANTIPLATELET ACTIVITY, AMINOCARBONYLATION, CO SOURCE",
author = "Evgeny Tretyakov and Ashok Keerthi and Martin Baumgarten and Sergey Veber and Matvey Fedin and Dmitry Gorbunov and Inna Shundrina and Nina Gritsan",
note = "Publisher Copyright: {\textcopyright} 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.",
year = "2017",
month = oct,
day = "1",
doi = "10.1002/open.201700110",
language = "English",
volume = "6",
pages = "642--652",
journal = "ChemistryOpen",
issn = "2191-1363",
publisher = "John Wiley and Sons Inc.",
number = "5",

}

RIS

TY - JOUR

T1 - The Design of Radical Stacks

T2 - Nitronyl-Nitroxide-Substituted Heteropentacenes

AU - Tretyakov, Evgeny

AU - Keerthi, Ashok

AU - Baumgarten, Martin

AU - Veber, Sergey

AU - Fedin, Matvey

AU - Gorbunov, Dmitry

AU - Shundrina, Inna

AU - Gritsan, Nina

N1 - Publisher Copyright: © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

PY - 2017/10/1

Y1 - 2017/10/1

N2 - The first alkyl chain-anchored heteropentacene, dithieno[2,3-d;2′,3′-d′]benzo-[1,2-b;3,4-b′]dithiophene (DTmBDT), mono- or disubstituted with a nitronyl nitroxide group has been prepared through a cross-coupling synthetic procedure of the corresponding dibromo-derivative (Br2-DTmBDT) with a nitronyl nitroxide-2-ide gold(I) complex. The synthesized nitroxides possess high kinetic stability, which allowed us to investigate their structure and thermal, optical, electrochemical, and magnetic properties. Single-crystal X-ray diffraction of both mono- and diradicals revealed that the nitronyl nitroxide group lies almost in the same plane as the nearest side thiophene ring. Such arrangement favors formation of edge-to-edge dimers, which then form close π-stacks surrounded by interdigitating alkyl chains. Before melting, these nitronyl nitroxide radical substituted molecules undergo at least two different phase transitions (PTs): for the monoradical, PTs are reversible, accompanied by hysteresis, and occur near 13 and 83 °C; the diradical upon heating shows a reversible PT with hysteresis in the temperature range 2–11 °C and an irreversible PT near 135 °C. PTs of this type are absent in Br2-DTmBDT. Therefore, the step-by-step substitution of bromine atoms by nitronyl nitroxide groups changes the structural organization of DTmBDT and induces the emergence of PTs. This knowledge may facilitate crystal engineering of π-stacked paramagnets and related molecular spin devices.

AB - The first alkyl chain-anchored heteropentacene, dithieno[2,3-d;2′,3′-d′]benzo-[1,2-b;3,4-b′]dithiophene (DTmBDT), mono- or disubstituted with a nitronyl nitroxide group has been prepared through a cross-coupling synthetic procedure of the corresponding dibromo-derivative (Br2-DTmBDT) with a nitronyl nitroxide-2-ide gold(I) complex. The synthesized nitroxides possess high kinetic stability, which allowed us to investigate their structure and thermal, optical, electrochemical, and magnetic properties. Single-crystal X-ray diffraction of both mono- and diradicals revealed that the nitronyl nitroxide group lies almost in the same plane as the nearest side thiophene ring. Such arrangement favors formation of edge-to-edge dimers, which then form close π-stacks surrounded by interdigitating alkyl chains. Before melting, these nitronyl nitroxide radical substituted molecules undergo at least two different phase transitions (PTs): for the monoradical, PTs are reversible, accompanied by hysteresis, and occur near 13 and 83 °C; the diradical upon heating shows a reversible PT with hysteresis in the temperature range 2–11 °C and an irreversible PT near 135 °C. PTs of this type are absent in Br2-DTmBDT. Therefore, the step-by-step substitution of bromine atoms by nitronyl nitroxide groups changes the structural organization of DTmBDT and induces the emergence of PTs. This knowledge may facilitate crystal engineering of π-stacked paramagnets and related molecular spin devices.

KW - density functional and ab initio calculations

KW - EPR spectroscopy

KW - fused thiophene

KW - nitronyl nitroxides

KW - π-stacking

KW - DNA-PK

KW - COMPLEXES

KW - EX-SITU GENERATION

KW - OXIDATIVE ADDITION

KW - density functional and ab into calculations

KW - pi-stacking

KW - CARBON-MONOXIDE

KW - PALLADIUM-CATALYZED CARBONYLATION

KW - ARYL HALIDES

KW - ANTIPLATELET ACTIVITY

KW - AMINOCARBONYLATION

KW - CO SOURCE

UR - http://www.scopus.com/inward/record.url?scp=85028860292&partnerID=8YFLogxK

U2 - 10.1002/open.201700110

DO - 10.1002/open.201700110

M3 - Article

C2 - 29046859

AN - SCOPUS:85028860292

VL - 6

SP - 642

EP - 652

JO - ChemistryOpen

JF - ChemistryOpen

SN - 2191-1363

IS - 5

ER -

ID: 9032651