Deciphering the Novel Photoreactivity of β‐Enaminones

L Laura M. Obloy (Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA) L Lakshmy Kannadi Valloli (Center for Photochemical Sciences and Department of Chemistry) A Alejandro Blanco Gonzalez (Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA) D Dipti Garg (Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA) M Meseret Simachew Bezabih (Department of Chemistry) M Massimo Olivucci (Department of Biotechnology, Chemistry and Pharmacy, University of Siena, Siena, Italy.) A Alexander N. Tarnovsky (The Center for Photochemical Sciences) J Jayaraman Sivaguru (Center for Photochemical Sciences and Department of Chemistry)

Abstract

Abstract The mechanism of a newly discovered photochemical reaction of β‐enaminones is examined by femtosecond transient absorption spectroscopy and multistate multiconfigurational quantum chemical calculations. Our study reveals that this photochemical reaction features a previously undocumented excited‐state‐proton‐transfer (ESIPT) process. We show that this process is structurally and dynamically gated, occurring in ultrafast time domain with complex progression of β‐enaminone along three potential energy surfaces featuring two conical intersections and a singlet‐triplet crossing.

Article Details

Volume / Issue Vol. 65, Issue 1
Published January 02, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (8)

L

Laura M. Obloy

Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA

L

Lakshmy Kannadi Valloli

Center for Photochemical Sciences and Department of Chemistry

A

Alejandro Blanco Gonzalez

Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA

D

Dipti Garg

Center for Photochemical Sciences and Department of Chemistry Bowling Green State University Bowling Green OH 43403 USA

M

Meseret Simachew Bezabih

Department of Chemistry

M

Massimo Olivucci

Department of Biotechnology, Chemistry and Pharmacy, University of Siena, Siena, Italy.

A

Alexander N. Tarnovsky

The Center for Photochemical Sciences

J

Jayaraman Sivaguru

Center for Photochemical Sciences and Department of Chemistry