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A computational investigation of the photochemical oxaziridine and amide conversion process of open-chain conjugated nitrone with electron-withdrawing trifluoromethyl group on nitrogen

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Abstract

This computational study investigates the photo-excitation process and subsequent photoproduct formation steps through non-radiative deactivation channels in open-chain conjugated N-substituted nitrone systems (model compounds of corresponding retinylnitrones) having electron-withdrawing groups on nitrogen. Calculations mostly based on CASSCF/6-31G* and CASMP2/6-31G* level of theories on a representative system with N-trifluoromethyl substituent have predicted initial photo-excitation to a planar singlet state. This photochemical path is subsequently followed by a barrierless non-radiative channel towards the lowest-energy conical intersection (CI) geometry having a terminal CNO kink, and situated at 30 kcal/mol below the planar excited state. Following the direction of its gradient difference (GD) vectors, an oxaziridine-type species (R C−O=1.38 Å, R N−O=1.53 Å, < CNO =55.8∘) appears at 3–6 kcal mol −1 below the ground state nitrone system through a transition state (along its reverse direction of minimum-energy path), situated on the reaction pathway. This species with an elongated N-O bond seems to be heading towards an amide geometry. On the other hand, in the opposite GD vector direction a proper oxaziridine geometry has been obtained with a much shorter N-O bond distance (R N−O=1.42 Å).

CASSCF-based photochemical studies on conjugated nitrones with N-trifluoromethyl group have revealed a non-radiative decay route of the singlet excited state through a terminally twisted conical intersection. This eventually leads to an oxaziridine-type biradical species with an elongated N-O bond and it seems to be heading towards an amide as photoproduct.

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Acknowledgements

We gratefully acknowledge the financial support received from the Council of Scientific and Industrial Research (CSIR), Government of India, under the Scheme No. 01(2681)/12/EMR- II, for the present work.

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  1. Department of Chemistry, Birla Institute of Technology and Science (BITS), Pilani K K Birla Goa Campus, Goa, 403 726, India

    PRAVEEN SAINI & ANJAN CHATTOPADHYAY

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  1. PRAVEEN SAINI
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  2. ANJAN CHATTOPADHYAY
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Correspondence to ANJAN CHATTOPADHYAY.

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Supporting Information

Conical intersection geometries using (6,6) and (8,8) active spaces and figure S1; Cartesian coordinates of optimized geometries are available at www.ias.ac.in/chemsci.

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SAINI, P., CHATTOPADHYAY, A. A computational investigation of the photochemical oxaziridine and amide conversion process of open-chain conjugated nitrone with electron-withdrawing trifluoromethyl group on nitrogen. J Chem Sci 127, 1757–1768 (2015). https://doi.org/10.1007/s12039-015-0941-8

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