Adiabatic Intramolecular Hydrogen Atom Transfer in 2-[2-(2-Pyrrolyl)ethenyl]pyridine

Obi, Masaki; Sakuragi, Hirochika; Arai, Tatsuo

doi:10.1246/cl.1998.169

Cited by 23 publications

(16 citation statements)

References 3 publications

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“…This behaviour, probably owing to a large torsional barrier in the lowest excited states, consistent with the experimental results, resembles that reported for analogous compounds with the N atom in ortho position to the ethenic bridge. The occurrence of one-way photoisomerization (only in one direction) because of the preferential stabilization of one of the two geometrical isomers was first reported in 1973 [7] and then found in several dihetarylethenes [8][9][10][11][12][13][14][15][16][17][20][21][22][23][24][25][26][27][28]. In addition to the case of 1-styrylisoquinoline cited above [11], other interesting examples are 1-(2 0 -pyridyl)-2-phenylbutadiene [21,22] (see Section 10.4) and 1-(2 0 -pyridyl),2-(2 00 -indolyl)ethene [13,15,16].…”

Section: Control Of Radiative and Reactive Relaxationmentioning

confidence: 99%

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Effect of Intramolecular H‐Bond‐Type Interactions on the Photochemistry of Aza‐Stilbene‐Like Molecules

Bartocci

Mazzucato

Spalletti

2010

Hydrogen Bonding and Transfer in the Excited State

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It is well known that molecular photochemistry can be affected significantly by both intermolecular and intramolecular interactions, and that hydrogen bonding (HB) can play an important role in this respect. The abundant experimental and theoretical investigations reported in the literature on the role of the intramolecular hydrogen bond (IHB) in controlling the dynamics of excited molecules mainly refer to the process of hydrogen or proton transfer to a heteroatom acceptor under irradiation (a few representative examples are reported in Refs [1] to [6]). When the interaction of H with the accepting group is only moderately strong, the effect can be limited to favour specific conformations, geometrical configurations and deactivation channels of the excited molecule.Early work on the effect of intramolecular interactions on the cis-trans (Z-E) photoreaction of compounds containing isomerizable double bonds showed how IHB of moderate strength can control the direction and the extent of the photoreaction [7-11], inhibiting photoisomerization and enhancing competing relaxation processes, or vice versa. Later, detailed studies were carried out on diarylethenes bearing aza-aromatic groups, such as pyridyl, quinolyl, pyrrolyl and indolyl groups [12][13][14][15][16][17].When rotation around single bonds is operative, different conformations may display a different behaviour. It is well known that flexible molecules containing double bonds, such as 1,2-diarylethenes, can be found in fluid solution as a mixture of different conformational geometries (conformers or rotamers) that exist in dynamic equilibrium in the ground state (S 0 ). The competition between conjugative and steric effects leads

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Section: Control Of Radiative and Reactive Relaxationmentioning

confidence: 99%

“…Later, detailed studies were carried out on diarylethenes bearing aza-aromatic groups, such as pyridyl, quinolyl, pyrrolyl and indolyl groups [12][13][14][15][16][17].…”

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confidence: 99%

Effect of Intramolecular H‐Bond‐Type Interactions on the Photochemistry of Aza‐Stilbene‐Like Molecules

Bartocci

Mazzucato

Spalletti

2010

Hydrogen Bonding and Transfer in the Excited State

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“…Intramolecular hydrogen bonding also affected the isomerization behavior (8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19). Thus, 29-hydroxychalcone underwent one-way cis fi trans isomerization through intramolecular hydrogen atom transfer in the excited triplet state (8)(9)(10)(11).…”

Section: Introductionmentioning

confidence: 99%

“…Thus, 29-hydroxychalcone underwent one-way cis fi trans isomerization through intramolecular hydrogen atom transfer in the excited triplet state (8)(9)(10)(11). Furthermore, 1-(2-pyridyl)-2-(2-pyrroly)ethene underwent one-way trans fi cis isomerization in the excited singlet state due to the ultra fast deactivation from the excited state by way of intramolecular hydrogen bonding (12). The cis isomer underwent intramolecular hydrogen atom transfer in the excited singlet state as revealed by the observation of the fluorescence spectra at a considerably longer wavelength region with large Stokes-shift.…”

Section: Introductionmentioning

confidence: 99%

“…The cis isomer underwent intramolecular hydrogen atom transfer in the excited singlet state as revealed by the observation of the fluorescence spectra at a considerably longer wavelength region with large Stokes-shift. Thus, the aryl group and the hydrogen bonding affected the mode of isomerization (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). All these compounds are expected to undergo isomerization around the C¼ ¼C double bond by 1808 rotation.…”

Section: Introductionmentioning

confidence: 99%

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Photoisomerization of Stilbene Dendrimers: The Need for a Volume-conserving Isomerization Mechanism¶

Uda

Mizutani

Hayakawa

et al. 2002

Photochem Photobiol

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Highly branched stilbene dendrimers were synthesized and their photochemical behavior was studied. Even the stilbene dendrimer with molecular weight over 6500 underwent trans-cis isomerization in the excited singlet state within the lifetime of 10 ns. The photoisomerization of C=C double bond of stilbene dendrimers in the excited state may proceed by a volume-conserving novel mechanism such as hula-twist rather than conventional 180 degrees rotation around the C=C double bond based on fluorescence and isomerization experiments.

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Control of photoisomerization of CC double bond by hydrogen bonding and photoinduced hydrogen atom transfer

Azechi

Takemura

Shinohara

et al. 2007

J of Physical Organic Chem

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Olefins with a phenathroline ring and a pyrrole ring were prepared and hydrogen atom transfer reaction in the excited singlet state was observed. The tautomer produced in the excited singlet state has lifetime of 30–50 ps for cis‐1 and c,t‐2 and with fluorescence maximum at longer wavelength region at 640 nm. The compound 1 exhibited photochromic behavior with its absorption maximum changing between 380 nm and 440 nm, while 2 exhibited only the small change of the absorption spectra on photoirradiation. Copyright © 2007 John Wiley & Sons, Ltd.

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Adiabatic Intramolecular Hydrogen Atom Transfer in 2-[2-(2-Pyrrolyl)ethenyl]pyridine

Cited by 23 publications

References 3 publications

Effect of Intramolecular H‐Bond‐Type Interactions on the Photochemistry of Aza‐Stilbene‐Like Molecules

Effect of Intramolecular H‐Bond‐Type Interactions on the Photochemistry of Aza‐Stilbene‐Like Molecules

Photoisomerization of Stilbene Dendrimers: The Need for a Volume-conserving Isomerization Mechanism¶

Control of photoisomerization of CC double bond by hydrogen bonding and photoinduced hydrogen atom transfer

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