1. Dithia[9]helicenes: Molecular design, surface imaging, and circularly polarized luminescence with enhanced dissymmetry factors
- Author
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Bianca C. Baciu, Pawel J. Bronk, Tamara de Ara, Rafael Rodriguez, Pierpaolo Morgante, Nicolas Vanthuyne, Carlos Sabater, Carlos Untiedt, Jochen Autschbach, Jeanne Crassous, Albert Guijarro, Universidad de Alicante. Departamento de Química Orgánica, Universidad de Alicante. Departamento de Física Aplicada, Universidad de Alicante. Instituto Universitario de Síntesis Orgánica, Nuevos Materiales y Catalizadores (MATCAT), Grupo de Nanofísica, Universidad de Alicante, Consejo Superior de Investigaciones Científicas [Spain] (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), State University of New York [Buffalo], Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Spanish MICIIN [PID2019-109539GB-C41], Generalitat Valenciana [PROMETEO/2021/017, CDEIGENT2018/028], University of Alicante [VIGROB-285], National Science Foundation [CHE-1855470], and Xunta de Galicia
- Subjects
Molecular design ,Circularly polarized luminescence ,Materials Chemistry ,Surface imaging ,[CHIM]Chemical Sciences ,Dithia[9]helicenes ,Enhanced dissymmetry factors ,General Chemistry - Abstract
We have carried out the synthesis of two dithia[9]helicenes by means of a LED-based double photocyclization. The compounds have sulfur atoms placed at the terminal rings of the helicene, and they display two alternative C2-symmetrical arrangements named exo (1) and endo (2). Separation of enantiomers of opposite helicity allowed the complete characterization of their chiroptical properties in solution, in silico, by X-ray crystallography, and adsorbed on gold. The theoretical analysis confirms the unexpected finding that endo-dithia[9]helicene displays an experimental dissymmetry factor in CPL (glum) larger than its isomer, exo-dithia[9]helicene. This enhanced glum factor ranks among the largest for a helicene-type molecule. Comparison with smaller analogues, namely exo and endo-dithia[7]helicenes (10 and 11, respectively), is also presented. AG and CU thank the financial support by the Spanish MICIIN (PID2019-109539GB-C41), the Generalitat Valenciana (PROMETEO/2021/017), and the University of Alicante (VIGROB-285). CS thanks for the financial support by the Generalitat Valenciana through CDEIGENT2018/028. The computational resources provided by the Department of Applied Physics of the University of Alicante are greatly appreciated. JA and PM thank the National Science Foundation, grant CHE-1855470, for support of the theoretical component of this study, and the Center for Computational Research (CCR) at UB for providing computational resources. J.C. thanks the the Ministère de l’Education Nationale, de la Recherche et de la Technologie and the Centre National de la Recherche Scientifique (CNRS).
- Published
- 2022