Supramolecular solids as a medium for single-crystal-to-single-crystal E/Z photoisomerization

Kinetic study of the photoreactions of two Zn-coordinated tiglic acid molecules

Shao Liang Zheng, Christophe M.L.Vande Velde, Marc Messerschmidt, Anatoliy Volkov, Milan Gembicky, Philip Coppens

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

[Zn(TA)2(H2O)2] (H-TA = tiglic acid) has been embedded in a framework composed of CECR (CECR = C-ethylcalix[4] resorcinarene) molecules to examine its E→Z photoisomerization in a periodic framework. The photoisomerization of tiglic acid in CECR-[Zn(TA) 2(H2O)2]·4H2O proceeds without the [2 + 2]-dimerization reaction that often occurs in crystals of uncomplexed analogues, and without breakdown of the crystal lattice thatfrequently occurs in neat crystals. The two Zn-coordinated TA molecules are located in different size cavities. The rate constants of the isomerization reaction are strongly affected by the size of the reaction cavity. Analysis of the temperature dependence of the reaction rates and the occupancies in the final photostationary state shows that the activation energies and the standard enthalpies of activation are dependent on the difference between the reaction cavities. This is the first quantitative diffraction study of solid-state E/Z isomerization of a metal-coordinated ligand in a periodic host environment.

Original languageEnglish (US)
Pages (from-to)706-713
Number of pages8
JournalChemistry - A European Journal
Volume14
Issue number2
DOIs
StatePublished - Jan 23 2008
Externally publishedYes

Fingerprint

Photoisomerization
Isomerization
Single crystals
Crystals
Molecules
Kinetics
Dimerization
Acids
Crystal lattices
Reaction rates
Enthalpy
Rate constants
Activation energy
Diffraction
Metals
Chemical activation
Ligands
Temperature
tiglic acid
C-ethylcalix(4)resorcinarene

Keywords

  • Host-guest systems
  • Inclusion compounds
  • Photoisomerization
  • Reaction cavity

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Supramolecular solids as a medium for single-crystal-to-single-crystal E/Z photoisomerization : Kinetic study of the photoreactions of two Zn-coordinated tiglic acid molecules. / Zheng, Shao Liang; Velde, Christophe M.L.Vande; Messerschmidt, Marc; Volkov, Anatoliy; Gembicky, Milan; Coppens, Philip.

In: Chemistry - A European Journal, Vol. 14, No. 2, 23.01.2008, p. 706-713.

Research output: Contribution to journalArticle

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