TY - JOUR
T1 - Intramolecular nitro-assisted proton transfer in photoirradiated 2-(2′,4′-dinitrobenzyl)pyridine
T2 - Polarized optical spectroscopic study and electronic structure calculations
AU - Naumov, Panče
AU - Sakurai, Kenji
AU - Ishikawa, Tadahiko
AU - Takahashi, Junichi
AU - Koshihara, Shin Ya
AU - Ohashi, Yuji
PY - 2005/8/18
Y1 - 2005/8/18
N2 - The nitro-assisted proton transfer (NAPT), responsible for the photoactivity of ortho-nitrobenzylpyridines and a model for the nitro-based caged compounds, is studied along with the parent compound 2-(2′,4′- dinitrobenzyl)pyridine (DNBP) with polarized optical spectroscopy and theoretical calculations. The transition dipole moments of a DNBP single-crystal identified oriented molecules of the long-lived enamine tautomer (NH), rather than of the aci-nitro tautomer (OH), as carriers of the photoinduced blue coloration. It is clarified that the blue second singlet transition owes to intramolecular charge transfer from the allyl-pyridinium part to the dinitrophenyl fragment of NH. The theoretical modeling of the ground-state potential energy surface showed that while NH and OH can interconvert by means of direct proton transfer, such a process between the initial form CH and either OH and NH would require significant rotation of the aromatic rings. In the ground state, OH is less stable but the kinetically preferred product over NH. Once created, regardless of whether via ground-state or excited-state routes, the aci-nitro group of OH undergoes energetically inexpensive rotation to deliver the proton to the nitrogen acceptor. The "softening" of the energy surface around OH due to its structural flexibility, that is, mediation of the proton transfer by the nitro group, is crucial to overcome the high barrier for a direct proton jump from CH to NH, even in cases of unfavorable donor-acceptor geometry. The very small structural change experienced by the surrounding of a molecule undergoing NAPT is promising for the design of photoactive systems which retain their crystallinity during a prolonged operation.
AB - The nitro-assisted proton transfer (NAPT), responsible for the photoactivity of ortho-nitrobenzylpyridines and a model for the nitro-based caged compounds, is studied along with the parent compound 2-(2′,4′- dinitrobenzyl)pyridine (DNBP) with polarized optical spectroscopy and theoretical calculations. The transition dipole moments of a DNBP single-crystal identified oriented molecules of the long-lived enamine tautomer (NH), rather than of the aci-nitro tautomer (OH), as carriers of the photoinduced blue coloration. It is clarified that the blue second singlet transition owes to intramolecular charge transfer from the allyl-pyridinium part to the dinitrophenyl fragment of NH. The theoretical modeling of the ground-state potential energy surface showed that while NH and OH can interconvert by means of direct proton transfer, such a process between the initial form CH and either OH and NH would require significant rotation of the aromatic rings. In the ground state, OH is less stable but the kinetically preferred product over NH. Once created, regardless of whether via ground-state or excited-state routes, the aci-nitro group of OH undergoes energetically inexpensive rotation to deliver the proton to the nitrogen acceptor. The "softening" of the energy surface around OH due to its structural flexibility, that is, mediation of the proton transfer by the nitro group, is crucial to overcome the high barrier for a direct proton jump from CH to NH, even in cases of unfavorable donor-acceptor geometry. The very small structural change experienced by the surrounding of a molecule undergoing NAPT is promising for the design of photoactive systems which retain their crystallinity during a prolonged operation.
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U2 - 10.1021/jp0520392
DO - 10.1021/jp0520392
M3 - Article
C2 - 16834092
AN - SCOPUS:24644511253
SN - 1089-5639
VL - 109
SP - 7264
EP - 7275
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 32
ER -