Capturing Conformation-Dependent Photoreactivity of Crystalline 3-Azido-1,3-diphenylisobutyrophenone

Sambath Karthik, Kosala R.S. Thenna-Hewa, Dylan J. Shields, Jinhao Liu, Jeanette A. Krause, Anna D. Gudmundsdottir

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Solid-state photolysis of 3-azido-1,3-diphenyl-isobutyrophenone 1 results in selective formation of isobutyrophenone 2 and benzonitrile 3. X-ray structure analysis of azide 1 demonstrates that the conformer (1Cr) adopted for packing in the crystal lattice has the carbonyl moiety perpendicular to the α-phenyl group (Ph-C=O torsional angle of 85°). Laser flash photolysis of azide 1 nanocrystals allows direct detection of the lowest excited triplet ketone (TK) of 1Cr (λmax≈475 nm). Thus, in crystals, 1 is proposed to react via the TK state to cleave the Cβ−Cγ bond. Time-dependent density functional theory (TD-DFT) calculations verify that the energy of the TK of 1Cr is 79 kcal mol−1 above the ground state (S0), and thus TK has sufficient energy for cleavage of the Cβ−Cγ bond to form products 2 and 3, further supporting this solid-state reaction mechanism.

Original languageEnglish (US)
Pages (from-to)408-414
Number of pages7
JournalChemPhotoChem
Volume1
Issue number9
DOIs
StatePublished - Sep 1 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Analytical Chemistry

Keywords

  • density functional calculations
  • laser flash photolysis
  • photochemistry
  • reaction mechanisms
  • solid-state reactions

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