Single-crystal-to-single-crystal <i>E</i> → <i>Z</i> isomerization of tiglic acid in a supramolecular framework

Zheng, Shao Liang; Messerschmidt, Marc; Coppens, Philip

doi:10.1107/s0108768107018538

Cited by 33 publications

(25 citation statements)

References 31 publications

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“…Therefore, one can augment the maximum fraction of excitation possible above which crystal fracture occurs (see x3). Various studies have been carried out, including the nice recent example of an E-to-Z photoisomerization in 2,3-dimethylacrylic acid when encased within a calixarene molecular framework (Zheng et al, 2007).…”

Section: Steady-state Photo-structural Changes: Resultsmentioning

confidence: 99%

Photocrystallography

Cole

2007

Acta Cryst Sect A

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This review describes the development and application of a new crystallographic technique that is starting to enable the three-dimensional structural determination of molecules in their photo-activated states. So called 'photocrystallography' has wide applicability, particularly in the currently exciting area of photonics, and a discussion of this applied potential is put into context in this article. Studies are classified into four groups: photo-structural changes that are (i) irreversible; (ii) long-lived but reversible under certain conditions; (iii) transient with photo-active lifetimes of the order of microseconds; (iv) very short lived, existing at the nanosecond or even picosecond level. As photostructural changes relative to the 'ground state' can be subtle, this article necessarily concentrates on small-molecule single-crystal X-ray diffraction given that high atomic resolution is possible. That said, where it is pertinent, references are also made to related major advances in photo-induced macromolecular crystallography. The review concludes with an outlook on this new research area, including the future possibility of studying even more ephemeral, femtosecond-lived, photo-active species.

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Section: Steady-state Photo-structural Changes: Resultsmentioning

confidence: 99%

Photocrystallography

Cole

2007

Acta Cryst Sect A

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“…[36] In the smaller cavity the TA ligand is more restrained and the Z!E "back" isomerization is favored over the E!Z reaction, as a result an equal distribution is not reached. [18,19] The external shape of the crystal and its color are not affected by the exposure ( Figure S2, Supporting Information), even though the conversion percentage is considerable and both the shape of the guest and its position are affected by the photoisomerization. However, the final R factors (Table S1, Supporting Information) increase on exposure, which is attributed to radiation damage rather than to the isomerization.…”

Section: E!z Photoisomerizationsmentioning

confidence: 96%

“…However, the final R factors (Table S1, Supporting Information) increase on exposure, which is attributed to radiation damage rather than to the isomerization. [18] …”

Section: E!z Photoisomerizationsmentioning

confidence: 97%

“…[18,19,26,27] In addition, isolation of a molecule in a supramolecular complex prevents the [2 + 2] dimerization or polymerization which frequently occur when C=C bonds are stacked in a parallel (or anti-parallel) fashion in crystals. [28] In preceding work we reported the SCSC E/Z isomerization of the E modification of (E)-2-methylbut-2-enoic acid, tiglic acid (HTA, see below) and chloroacrylic acid embedded in a CECR framework (CECR = C-ethylcalix [4]resorcinarene), [18,19] the latter reaction starting from both the pure Z and the pure E isomers. Here, we present the first example of the SCSC E!Z isomerization of a molecule ligated to a group IIB metal atom within a supramolecular frame-…”

Section: A C H T U N G T R E N N U N G (H 2 O)mentioning

confidence: 99%

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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

Velde

Messerschmidt

et al. 2007

Chemistry A European J

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[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]4 H2O proceeds without the [2+2]-dimerization reaction that often occurs in crystals of uncomplexed analogues, and without breakdown of the crystal lattice that frequently 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.

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“…In the recent decade the papers on monitoring photochemical reactions in crystals by means of X-ray structure analysis have started to appear in the scientific literature [1][2][3][4][5][6][7][8][9][10][11][12]. Those papers have provided the knowledge on structural changes brought about by photochemical reactions, in particular in a reaction center and positions of molecules in crystals.…”

Section: Introductionmentioning

confidence: 99%

Monitoring Structural Transformations in Crystals. Part 15. Structural Changes in Crystals Caused by UV Radiation Despite the Lack of a Photochemical Reaction

2012

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Crystals of 3-benzoylbicyclo[2.2.1]heptane-2-carboxylic acid (C 15 H 16 O 3 ) do not undergo the photochemical reaction, namely the Yang photocyclization, but they undergo UV radiation damage. The initial stages of this process were monitored by X-ray diffraction and structure analysis. The results show that the process is smooth and accompanied by the decrease of the overall scale factor, the certain increase of width of reflections, the increase of the cell parameters, intermolecular distances, atomic displacement parameters and the small changes in orientation of molecular fragments.

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Single-crystal-to-single-crystal E → Z isomerization of tiglic acid in a supramolecular framework

Cited by 33 publications

References 31 publications

Photocrystallography

Photocrystallography

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

Monitoring Structural Transformations in Crystals. Part 15. Structural Changes in Crystals Caused by UV Radiation Despite the Lack of a Photochemical Reaction

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