Unprecedented Isomerism-Activity Relation in Molecular Electrocatalysis

Kottaichamy, AR and Begum, S and Nazrulla, MA and Dargily, NC and Devendrachari, MC and Manzoor Bhat, Z and Thimmappa, R and Makri Nimbegondi Kotresh, H and Vinod, CP and Thotiyl, MO (2020) Unprecedented Isomerism-Activity Relation in Molecular Electrocatalysis. In: Journal of Physical Chemistry Letters, 11 (1). pp. 263-271.

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Abstract

The role of electrocatalysts in energy storage/conversion, biomedical and environmental sectors, green chemistry, and much more has generated enormous interest in comprehending their structure-activity relations. While targeting the surface-to-volume ratio, exposing reactive crystal planes and interfacial modifications are time-tested considerations for activating metallic catalysts; it is primarily by substitution in molecular electrocatalysts. This account draws the distinction between a substituent's chemical identity and isomerism, when regioisomerism of the -NO2 substituent is conferred at the "α" and "β" positions on the macrocycle of cobalt phthalocyanines. Spectroscopic analysis and theoretical calculations establish that the β isomer accumulates catalytically active intermediates via a cumulative influence of inductive and resonance effects. However, the field effect in the α isomer restricts this activation due to a vanishing resonance effect. The demonstration of the distinct role of isomerism in substituted molecular electrocatalysts for reactions ranging from energy conversion to biosensing highlights that isomerism of the substituents makes an independent contribution to electrocatalysis over its chemical identity.

Item Type:	Journal Article
Publication:	Journal of Physical Chemistry Letters
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Catalysis; Chemical activation; Electrocatalysis; Electrocatalysts; Electrolysis; Energy conversion; Spectroscopic analysis; Stereochemistry, Cobalt phthalocyanine; Cumulative influence; Environmental sector; Independent contributions; Interfacial modification; Structure-activity relation; Surface-to-volume ratio; Theoretical calculations, Isomers
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	06 Feb 2023 10:17
Last Modified:	06 Feb 2023 10:17
URI:	https://eprints.iisc.ac.in/id/eprint/79942

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