抄録
When a 1:1 complex of cis-3,3′-bis(diphenylhydroxymethyl)stilbene (1) with acetone was irradiated in the solid state at room temperature using a high-pressure mercury lamp with a Pyrex filter for 6 h, a 1:1 complex of the trans-isomer (2) with acetone was obtained without losing the guest acetone molecules. Similar results were obtained without a guest or in the presence of other guests. Internal rotation around the double bond bearing the very large triphenylhydroxymethyl substituent is hardly imaginable in the confinement of the crystal. Therefore, the geometrically easier 'hula-twist' (HT) mechanism with its movements primarily in the molecular plane provides a viable mechanistic alternative for the cis-trans isomerization. The solid-state mechanism of the reaction was studied by x-ray and atomic force microscopy (AFM) analyses. Face-selective efflorescence formed a protective cover on (100) and can be related to the crystal structure. Further molecular migration was not detected with the sensitivity of AFM and the crystal of 1·acetone did not lose its clarity and microscopic shape. The cis-trans conversion profits from cages that are present in the crystal lattice. X-ray structural analysis confirmed a strong loss of crystallinity upon the photochemical conversion of 1·acetone which precludes a definitive conformational proof of HT by x-ray diffraction. The formation of the amorphous phase excludes a topotactic reaction.
| 元の言語 | English |
|---|---|
| ページ（範囲） | 905-912 |
| ページ数 | 8 |
| ジャーナル | Journal of Physical Organic Chemistry |
| 巻 | 16 |
| 発行部数 | 12 |
| DOI | |
| 出版物ステータス | Published - 2003 12 |
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ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
これを引用
Unidirectional cis-trans photoisomerization of cis-3,3′-bis(diphenylhydroxymethyl)stilbene in inclusion complex crystals. / Tanaka, Koichi; Hiratsuka, Takaichi; Ohba, Shigeru; Naimi-Jamal, M. Reza; Kaupp, Gerd.
：: Journal of Physical Organic Chemistry, 巻 16, 番号 12, 12.2003, p. 905-912.研究成果: Article
}
TY - JOUR
T1 - Unidirectional cis-trans photoisomerization of cis-3,3′-bis(diphenylhydroxymethyl)stilbene in inclusion complex crystals
AU - Tanaka, Koichi
AU - Hiratsuka, Takaichi
AU - Ohba, Shigeru
AU - Naimi-Jamal, M. Reza
AU - Kaupp, Gerd
PY - 2003/12
Y1 - 2003/12
N2 - When a 1:1 complex of cis-3,3′-bis(diphenylhydroxymethyl)stilbene (1) with acetone was irradiated in the solid state at room temperature using a high-pressure mercury lamp with a Pyrex filter for 6 h, a 1:1 complex of the trans-isomer (2) with acetone was obtained without losing the guest acetone molecules. Similar results were obtained without a guest or in the presence of other guests. Internal rotation around the double bond bearing the very large triphenylhydroxymethyl substituent is hardly imaginable in the confinement of the crystal. Therefore, the geometrically easier 'hula-twist' (HT) mechanism with its movements primarily in the molecular plane provides a viable mechanistic alternative for the cis-trans isomerization. The solid-state mechanism of the reaction was studied by x-ray and atomic force microscopy (AFM) analyses. Face-selective efflorescence formed a protective cover on (100) and can be related to the crystal structure. Further molecular migration was not detected with the sensitivity of AFM and the crystal of 1·acetone did not lose its clarity and microscopic shape. The cis-trans conversion profits from cages that are present in the crystal lattice. X-ray structural analysis confirmed a strong loss of crystallinity upon the photochemical conversion of 1·acetone which precludes a definitive conformational proof of HT by x-ray diffraction. The formation of the amorphous phase excludes a topotactic reaction.
AB - When a 1:1 complex of cis-3,3′-bis(diphenylhydroxymethyl)stilbene (1) with acetone was irradiated in the solid state at room temperature using a high-pressure mercury lamp with a Pyrex filter for 6 h, a 1:1 complex of the trans-isomer (2) with acetone was obtained without losing the guest acetone molecules. Similar results were obtained without a guest or in the presence of other guests. Internal rotation around the double bond bearing the very large triphenylhydroxymethyl substituent is hardly imaginable in the confinement of the crystal. Therefore, the geometrically easier 'hula-twist' (HT) mechanism with its movements primarily in the molecular plane provides a viable mechanistic alternative for the cis-trans isomerization. The solid-state mechanism of the reaction was studied by x-ray and atomic force microscopy (AFM) analyses. Face-selective efflorescence formed a protective cover on (100) and can be related to the crystal structure. Further molecular migration was not detected with the sensitivity of AFM and the crystal of 1·acetone did not lose its clarity and microscopic shape. The cis-trans conversion profits from cages that are present in the crystal lattice. X-ray structural analysis confirmed a strong loss of crystallinity upon the photochemical conversion of 1·acetone which precludes a definitive conformational proof of HT by x-ray diffraction. The formation of the amorphous phase excludes a topotactic reaction.
KW - Amorphous phase
KW - Atomic force microscopy
KW - cis-trans isomerization
KW - Hula-twist
KW - Inclusion crystal
KW - X-ray structure
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U2 - 10.1002/poc.693
DO - 10.1002/poc.693
M3 - Article
AN - SCOPUS:0344861816
VL - 16
SP - 905
EP - 912
JO - Journal of Physical Organic Chemistry
JF - Journal of Physical Organic Chemistry
SN - 0894-3230
IS - 12
ER -