PHOTOISOMERIZATION OF (CYANOMETHYLENE)CYCLOPROPANE (C₅H₅N) IN A LOW TEMPERATURE RARE GAS MATRIX

Wood, Samuel A.

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Description

Title

PHOTOISOMERIZATION OF (CYANOMETHYLENE)CYCLOPROPANE (C₅H₅N) IN A LOW TEMPERATURE RARE GAS MATRIX

Author(s)

Wood, Samuel A.

Contributor(s)

• McMahon, Robert J.
• Woods, R. Claude
• Esselman, Brian J.
• Kougias, Samuel M.

Issue Date

2023-06-22

Keyword(s)

Photodissociation and photochemistry

Abstract

The C₅H₅N potential energy surface is experimentally and computationally investigated through matrix isolation photolysis of 1-cyano-2-methylenecyclopropane, a pyridine isomer containing nitrile and methylenecyclopropane functional groups. Synthesis of the novel isomer 1-cyano-2-methylenecyclopropane, presented here for the first time, involves dehydration of the corresponding amide. 1-Cyano-2-methylenecyclopropane is also generated upon photoisomerization (λ>200 nm) of (cyanomethylene)cyclopropane in argon at 19 K. Under these irradiation conditions, the photoisomerization favors the formation of 1-cyano-2-methylenecyclopropane, for which the UV absorption is blue-shifted, relative to (cyanomethylene)cyclopropane. The solution-phase UV-vis spectra and matrix-isolation IR spectra of both pure species are presented and compared to predicted spectra obtained using TD-DFT and anharmonic vibrational frequency calculations, respectively. Photoisomerization to pyridine was not observed.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Handle URL

https://hdl.handle.net/2142/122343

DOI

https://doi.org/10.15278/isms.2023.6884

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