The application of molecular modelling techniques in the prediction of the photochromic behaviour of spiroindolinonaphthoxazines

Robert M. Christie, Li J. Chi, Roger A. Spark, Keith M. Morgan, A. S F Boyd, Antonin Lycka

Research output: Contribution to journalArticle

Abstract

Two isomeric photochromic compounds, spiroindolinonaphth[2,1-b] [1,4] oxazine 1 and spiroindolinonaphth[1,2-b] [1,4] oxazine 2, were synthesised. During the synthesis of spirooxazine 2, a coloured, non-photochromic spirooxazine 6 was isolated as an associated product and characterised as a mixture of geometric isomers. A range of readily available molecular modelling techniques were applied to provide an account of the behaviour of the photochromic materials. Heats of formation calculated using AM1, following MM2 geometry optimisation, for ring-closed and ring-opened spirooxazines, provide a method for assessing whether a spirooxazine might be expected to show photochromic behaviour. ZINDO calculations based on the molecular geometry optimised in this way provide a reasonable account of the UV-vis absorption profile of the ring-closed forms 1 and 2. An approach that uses MM2 calculations to predict the most stable of the isomer(s) of the transient ring-opened photomerocyanines, used in combination with PPP-MO calculations using optimised parameterisation, may be used to provide a prediction of the ?max values, although the method may not produce an unequivocal result when the energies of the geometrical isomers are similar. © 2004 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)37-45
Number of pages9
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume169
Issue number1
DOIs
Publication statusPublished - 1 Jan 2005

Fingerprint

Molecular modeling
Isomers
Oxazines
Geometry
Parameterization

Keywords

  • Molecular modelling
  • Photochromism
  • Photomerocyanine
  • Spirooxazine

Cite this

Christie, Robert M. ; Chi, Li J. ; Spark, Roger A. ; Morgan, Keith M. ; Boyd, A. S F ; Lycka, Antonin. / The application of molecular modelling techniques in the prediction of the photochromic behaviour of spiroindolinonaphthoxazines. In: Journal of Photochemistry and Photobiology A: Chemistry. 2005 ; Vol. 169, No. 1. pp. 37-45.
@article{355453342ee249c0860267dfe3c8f902,
title = "The application of molecular modelling techniques in the prediction of the photochromic behaviour of spiroindolinonaphthoxazines",
abstract = "Two isomeric photochromic compounds, spiroindolinonaphth[2,1-b] [1,4] oxazine 1 and spiroindolinonaphth[1,2-b] [1,4] oxazine 2, were synthesised. During the synthesis of spirooxazine 2, a coloured, non-photochromic spirooxazine 6 was isolated as an associated product and characterised as a mixture of geometric isomers. A range of readily available molecular modelling techniques were applied to provide an account of the behaviour of the photochromic materials. Heats of formation calculated using AM1, following MM2 geometry optimisation, for ring-closed and ring-opened spirooxazines, provide a method for assessing whether a spirooxazine might be expected to show photochromic behaviour. ZINDO calculations based on the molecular geometry optimised in this way provide a reasonable account of the UV-vis absorption profile of the ring-closed forms 1 and 2. An approach that uses MM2 calculations to predict the most stable of the isomer(s) of the transient ring-opened photomerocyanines, used in combination with PPP-MO calculations using optimised parameterisation, may be used to provide a prediction of the ?max values, although the method may not produce an unequivocal result when the energies of the geometrical isomers are similar. {\circledC} 2004 Elsevier B.V. All rights reserved.",
keywords = "Molecular modelling, Photochromism, Photomerocyanine, Spirooxazine",
author = "Christie, {Robert M.} and Chi, {Li J.} and Spark, {Roger A.} and Morgan, {Keith M.} and Boyd, {A. S F} and Antonin Lycka",
year = "2005",
month = "1",
day = "1",
doi = "10.1016/j.jphotochem.2004.06.006",
language = "English",
volume = "169",
pages = "37--45",
journal = "Journal of Photochemistry and Photobiology A: Chemistry",
issn = "1010-6030",
publisher = "Elsevier",
number = "1",

}

The application of molecular modelling techniques in the prediction of the photochromic behaviour of spiroindolinonaphthoxazines. / Christie, Robert M.; Chi, Li J.; Spark, Roger A.; Morgan, Keith M.; Boyd, A. S F; Lycka, Antonin.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 169, No. 1, 01.01.2005, p. 37-45.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The application of molecular modelling techniques in the prediction of the photochromic behaviour of spiroindolinonaphthoxazines

AU - Christie, Robert M.

AU - Chi, Li J.

AU - Spark, Roger A.

AU - Morgan, Keith M.

AU - Boyd, A. S F

AU - Lycka, Antonin

PY - 2005/1/1

Y1 - 2005/1/1

N2 - Two isomeric photochromic compounds, spiroindolinonaphth[2,1-b] [1,4] oxazine 1 and spiroindolinonaphth[1,2-b] [1,4] oxazine 2, were synthesised. During the synthesis of spirooxazine 2, a coloured, non-photochromic spirooxazine 6 was isolated as an associated product and characterised as a mixture of geometric isomers. A range of readily available molecular modelling techniques were applied to provide an account of the behaviour of the photochromic materials. Heats of formation calculated using AM1, following MM2 geometry optimisation, for ring-closed and ring-opened spirooxazines, provide a method for assessing whether a spirooxazine might be expected to show photochromic behaviour. ZINDO calculations based on the molecular geometry optimised in this way provide a reasonable account of the UV-vis absorption profile of the ring-closed forms 1 and 2. An approach that uses MM2 calculations to predict the most stable of the isomer(s) of the transient ring-opened photomerocyanines, used in combination with PPP-MO calculations using optimised parameterisation, may be used to provide a prediction of the ?max values, although the method may not produce an unequivocal result when the energies of the geometrical isomers are similar. © 2004 Elsevier B.V. All rights reserved.

AB - Two isomeric photochromic compounds, spiroindolinonaphth[2,1-b] [1,4] oxazine 1 and spiroindolinonaphth[1,2-b] [1,4] oxazine 2, were synthesised. During the synthesis of spirooxazine 2, a coloured, non-photochromic spirooxazine 6 was isolated as an associated product and characterised as a mixture of geometric isomers. A range of readily available molecular modelling techniques were applied to provide an account of the behaviour of the photochromic materials. Heats of formation calculated using AM1, following MM2 geometry optimisation, for ring-closed and ring-opened spirooxazines, provide a method for assessing whether a spirooxazine might be expected to show photochromic behaviour. ZINDO calculations based on the molecular geometry optimised in this way provide a reasonable account of the UV-vis absorption profile of the ring-closed forms 1 and 2. An approach that uses MM2 calculations to predict the most stable of the isomer(s) of the transient ring-opened photomerocyanines, used in combination with PPP-MO calculations using optimised parameterisation, may be used to provide a prediction of the ?max values, although the method may not produce an unequivocal result when the energies of the geometrical isomers are similar. © 2004 Elsevier B.V. All rights reserved.

KW - Molecular modelling

KW - Photochromism

KW - Photomerocyanine

KW - Spirooxazine

UR - http://www.scopus.com/inward/record.url?scp=8744287542&partnerID=8YFLogxK

U2 - 10.1016/j.jphotochem.2004.06.006

DO - 10.1016/j.jphotochem.2004.06.006

M3 - Article

VL - 169

SP - 37

EP - 45

JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

SN - 1010-6030

IS - 1

ER -