Alkyl-substituted bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophenes: weakening of intermolecular interactions and additive-assisted crystallization

Alkyl-substituted bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophenes: weakening of intermolecular interactions and additive-assisted crystallization Full article

Journal

CrystEngComm
ISSN: 1466-8033

Output data

Year: 2021, Volume: 23, Number: 14, Pages: 2654-2664 Pages count : 11 DOI: 10.1039/d0ce01794a

Authors

Sonina Alina A. ^1,2 , Becker Christina S. ¹ , Kuimov Anatoly D. ¹ , Shundrina Inna K. ¹ , Komarov Vladislav Yu. ³ , Kazantsev Maxim S. ¹

Affiliations

1	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Lavrentieva 9, Novosibirsk, 630090, Russian Federation
2	Novosibirsk State University, Pirogova 2, Novosibirsk, 630090, Russian Federation
3	A. V. Nikolaev Institute of Inorganic Chemistry, Lavrentieva 3, Novosibirsk, 630090, Russian Federation

Aggregation-induced emission (AIE) materials find their applications in organic optoelectronics, bio-imaging and sensors. In this work, we introduced alkyl substituents in AIE-active bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophene and elucidated their effect on the molecular and crystal structures, crystallization and optical properties of materials. Ethyl-containing (C2-BFMPT) and octyl-containing (C8-BFMPT) 2,5-bis(4-((2,7-dialkyl-9H-fluoren-9-ylidene)methyl)phenyl)thiophenes were synthesized in 4 steps. The introduction of alkyl groups weakened intermolecular interactions, decreased the crystal quality, melting point, and density, and increased the solubility of materials. Octyl-containing derivative was demonstrated to generate two crystal forms obtained by the native (form I) and additive-assisted (form II) crystallizations. The latter appeared to have a better crystal quality. C-H⋯π interactions and an extensive positional disorder were revealed for both derivatives. In C8-BFMPT crystals (form II) only a half of molecular backbones were well localized due to multiple intermolecular C-H⋯π interactions, whereas another half demonstrated a high positional disorder. The AIE effect with a negligible photoluminescence (PL) quantum yield (QY) in solution and a PL QY of 5% for C2-BFMPT and 2% for C8-BFMPT (form II) crystals was demonstrated. The cooling of the C8-BFMPT form II resulted in 10-fold increase of PL QY. The introduction of alkyl-substituents and additive-assisted crystallization are highlighted as powerful tools for the control of crystal packing, morphology, polymorphism and the optical performance of AIE-materials. © The Royal Society of Chemistry 2021.

Sonina A.A. , Becker C.S. , Kuimov A.D. , Shundrina I.K. , Komarov V.Y. , Kazantsev M.S.
Alkyl-substituted bis(4-((9H-fluoren-9-ylidene)methyl)phenyl)thiophenes: weakening of intermolecular interactions and additive-assisted crystallization
CrystEngComm. 2021. V.23. N14. P.2654-2664. DOI: 10.1039/d0ce01794a WOS Scopus РИНЦ

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