File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Water-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solution

TitleWater-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solution
Authors
Issue Date2013
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
The Journal of Organic Chemistry, 2013, v. 78 n. 11, p. 5677-5684 How to Cite?
AbstractAn unusual photochemistry of water-assisted self-photoredox of 3-(hydroxymethyl) benzophenone 1 has been investigated by CASPT2//CASSCF computations. The water-assisted self-photoredox is found to proceed via three sequential reactions: an excited-state intermolecular proton transfer (ESIPT), a photoinduced deprotonation, and a self-redox reaction. Upon photoexcitation at 243 nm, the system of 1 is taken to the Franck-Condon region of a short-distance charge transfer (SCT) state of S(SCT)((1)pipi*) and then undergoes ESIPT with a small barrier of approximately 3.4 kcal/mol producing the intermediate 2. Subsequently, the singlet-triplet crossing (STC) of STC ((1)pipi*/(3)pipi*) relays 2 by intersystem crossing to the T(SCT)((3)pipi*) state followed by a deprotonation reaction overcoming a moderate barrier of approximately 8.0 kcal/mol and finally produces the triplet biradical intermediate 3. Another moderate barrier ( approximately 5.8 kcal/mol) in the T(SCT)((3)pipi*) state has to be overcome so as to relax to a second singlet-triplet crossing STC(T/S0) that allows an efficient spin-forbidden decay to the ground state. The self-redox reaction aided by water molecules occurs with tiny barriers in the S0 state via two steps, protonation of the benzhydrol carbon to produce intermediate 4 and then deprotonation from the benzylic oxygen to yield the final product 3-formylbenzhydrol 5.
Persistent Identifierhttp://hdl.handle.net/10722/188229
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChen, X-
dc.contributor.authorZhang, Q-
dc.contributor.authorXu, Y-
dc.contributor.authorFang, W-
dc.contributor.authorPhillips, DL-
dc.date.accessioned2013-08-23T03:30:36Z-
dc.date.available2013-08-23T03:30:36Z-
dc.date.issued2013-
dc.identifier.citationThe Journal of Organic Chemistry, 2013, v. 78 n. 11, p. 5677-5684-
dc.identifier.issn0022-3263-
dc.identifier.urihttp://hdl.handle.net/10722/188229-
dc.description.abstractAn unusual photochemistry of water-assisted self-photoredox of 3-(hydroxymethyl) benzophenone 1 has been investigated by CASPT2//CASSCF computations. The water-assisted self-photoredox is found to proceed via three sequential reactions: an excited-state intermolecular proton transfer (ESIPT), a photoinduced deprotonation, and a self-redox reaction. Upon photoexcitation at 243 nm, the system of 1 is taken to the Franck-Condon region of a short-distance charge transfer (SCT) state of S(SCT)((1)pipi*) and then undergoes ESIPT with a small barrier of approximately 3.4 kcal/mol producing the intermediate 2. Subsequently, the singlet-triplet crossing (STC) of STC ((1)pipi*/(3)pipi*) relays 2 by intersystem crossing to the T(SCT)((3)pipi*) state followed by a deprotonation reaction overcoming a moderate barrier of approximately 8.0 kcal/mol and finally produces the triplet biradical intermediate 3. Another moderate barrier ( approximately 5.8 kcal/mol) in the T(SCT)((3)pipi*) state has to be overcome so as to relax to a second singlet-triplet crossing STC(T/S0) that allows an efficient spin-forbidden decay to the ground state. The self-redox reaction aided by water molecules occurs with tiny barriers in the S0 state via two steps, protonation of the benzhydrol carbon to produce intermediate 4 and then deprotonation from the benzylic oxygen to yield the final product 3-formylbenzhydrol 5.-
dc.languageeng-
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc-
dc.relation.ispartofThe Journal of Organic Chemistry-
dc.titleWater-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solutionen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.doi10.1021/jo4008783-
dc.identifier.pmid23672423-
dc.identifier.hkuros220089-
dc.identifier.volume78-
dc.identifier.issue11-
dc.identifier.spage5677-
dc.identifier.epage5684-
dc.identifier.isiWOS:000320298700055-
dc.publisher.placeUnited States-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats