B.A. Hussein
Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes
Hussein, B.A.; Shakeel, Z.; Turley, A.T.; Bismillah, A.N.; Wolfstadt, K.; Pia, J.; Pilkington, M.; McGonigal, P.R.; Adler, M.
Authors
Z. Shakeel
A.T. Turley
A.N. Bismillah
K. Wolfstadt
J. Pia
M. Pilkington
Dr Paul Mcgonigal paul.mcgonigal@durham.ac.uk
Academic Visitor
M. Adler
Abstract
Porphyrins are cornerstone functional materials that are useful in a wide variety of settings, ranging from molecular electronics to biology and medicine. Their applications are often hindered, however, by poor solubilities that result from their extended, solvophobic aromatic surfaces. Attempts to counteract this problem by functionalizing their peripheries have been met with only limited success. Here, we demonstrate a versatile strategy to tune the physical and electronic properties of porphyrins using an axial functionalization approach. Porphyrin silanes (PorSils) and bissilyloxy PorSils (SOPS) are prepared from porphyrins by operationally simple κ4N-silylation protocols, introducing bulky silyloxy “caps” that are central and perpendicular to the planar porphyrin. While porphyrins typically form either J- or H-aggregates, SOPS do not self-associate in the same manner: the silyloxy axial substituents dramatically improve the solubility by inhibiting aggregation. Moreover, axial porphyrin functionalization offers convenient handles through which optical, electronic, and structural properties of the porphyrin core can be modulated. We observe that the identity of the silyloxy substituent impacts the degree of planarity of the porphyrin in the solid state as well as the redox potentials.
Citation
Hussein, B., Shakeel, Z., Turley, A., Bismillah, A., Wolfstadt, K., Pia, J., …Adler, M. (2020). Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes. Inorganic Chemistry, 59(18), 13533-13541. https://doi.org/10.1021/acs.inorgchem.0c01891
Journal Article Type | Article |
---|---|
Acceptance Date | Aug 12, 2020 |
Online Publication Date | Aug 30, 2020 |
Publication Date | 2020 |
Deposit Date | Aug 13, 2020 |
Publicly Available Date | Aug 30, 2021 |
Journal | Inorganic Chemistry |
Print ISSN | 0020-1669 |
Electronic ISSN | 1520-510X |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 59 |
Issue | 18 |
Pages | 13533-13541 |
DOI | https://doi.org/10.1021/acs.inorgchem.0c01891 |
Public URL | https://durham-repository.worktribe.com/output/1258540 |
Related Public URLs | https://chemrxiv.org/articles/Control_of_Porphyrin_Planarity_and_Aggregation_by_Covalent_Capping_Bissilyloxy_Porphyrin_Silanes/12195084 |
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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, 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/acs.inorgchem.0c01891
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