Dual-mode chiral self-assembly of cone-shaped subphthalocyanine aromatics
Entity
UAM. Departamento de Química OrgánicaPublisher
American Chemical SocietyDate
2020-11-13Citation
10.1021/jacs.0c07291
Journal of the American Chemical Society (JACS) 142.50 (2020): 21017-21031
ISSN
0002-7863 (print); 1520-5126 (online)DOI
10.1021/jacs.0c07291Funded by
Funding from the Spanish MINECO/MCIU [PGC2018-099568-B-I00, CTQ2017-85393-P, CTQ2017-84727-P, ERA-NET/European Commission/MINECO (UNIQUE, SOLAR-ERA.NET Cofund 2 N° 008/ PCI2019-111889-2), and RED2018-102331-T], the Generalitat Valenciana (SEJI/2018/035), and European Feder funds (PGC2018-099568-B-I00) is gratefully acknowledged. IMDEA Nanocien-cia acknowledges support from the “Severo Ochoa” Pro-gramme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686)Project
Gobierno de España. PGC2018-099568-B-I00; Gobierno de España. CTQ2017-85393-P; Gobierno de España. CTQ2017-84727-P; Gobierno de España. PCI2019-111889-2; Gobierno de España. RED2018-102331-T; Gobierno de España. PGC2018-099568-B-I00; Gobierno de España. SEV-2016-0686Editor's Version
https://doi.org/10.1021/jacs.0c07291Subjects
Self-assembly; Subphthalocyanine; Supramolecular Polymers; Porphyrinoids; QuímicaNote
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.0c07291Rights
© 2020 American Chemical SocietyAbstract
Columnar polymers and liquid crystals obtained from π-conjugated cone-shaped molecules are receiving increasing interest due to the possibility of obtaining unconventional polar organizations that show anisotropic charge transport and unique chiroptical properties. However, and in contrast to the more common planar discotics, the self-assembly of conic or pyramidic molecules in solution remains largely unexplored. Here, we show how a molecular geometry change, from flat to conic, can generate supramolecular landscapes where different self-assembled species, each of them being under thermodynamic equilibrium with the monomer, exist exclusively within distinct regimes. In particular, depending on the solvent nature-aromatic or aliphatic-cone-shaped C3-symmetric subphthalocyanine 1 can undergo self-assembly either as a tail-to-tail dimer, showing monomer-dimer sigmoidal transitions, or as a head-to-tail noncentrosymmetric columnar polymer, exhibiting a nucleation-elongation polymerization mechanism. Moreover, the experimental and theoretical comparison between racemic and enantiopure samples revealed that the two enantiomers (1M and 1P) tend to narcissistically self-sort in the dimer regime, each enantiomer showing a strong preference to associate with itself, but socially self-sort in the polymer regime, favoring an alternate stacking order along the columns
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Google Scholar:Mayoral, María J.
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Guilleme, Julia
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Calbo, Joaquín
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Aragó, Juan
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Aparicio, Fátima
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Ortí, Enrique
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Torres Cebada, Tomás
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González Rodríguez, David
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