File Download
There are no files associated with this item.
Links for fulltext
(May Require Subscription)
- Publisher Website: 10.1021/jo4008783
- Scopus: eid_2-s2.0-84879287218
- PMID: 23672423
- WOS: WOS:000320298700055
- Find via
Supplementary
- Citations:
- Appears in Collections:
Article: Water-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solution
Title | Water-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solution |
---|---|
Authors | |
Issue Date | 2013 |
Publisher | American 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? |
Abstract | An 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 Identifier | http://hdl.handle.net/10722/188229 |
ISSN | 2023 Impact Factor: 3.3 2023 SCImago Journal Rankings: 0.724 |
ISI Accession Number ID |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Chen, X | - |
dc.contributor.author | Zhang, Q | - |
dc.contributor.author | Xu, Y | - |
dc.contributor.author | Fang, W | - |
dc.contributor.author | Phillips, DL | - |
dc.date.accessioned | 2013-08-23T03:30:36Z | - |
dc.date.available | 2013-08-23T03:30:36Z | - |
dc.date.issued | 2013 | - |
dc.identifier.citation | The Journal of Organic Chemistry, 2013, v. 78 n. 11, p. 5677-5684 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.uri | http://hdl.handle.net/10722/188229 | - |
dc.description.abstract | An 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.language | eng | - |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc | - |
dc.relation.ispartof | The Journal of Organic Chemistry | - |
dc.title | Water-Assisted Self-Photoredox of 3-(Hydroxymethyl)benzophenone: An Unusual Photochemistry Reaction in Aqueous Solution | en_US |
dc.type | Article | en_US |
dc.identifier.email | Phillips, DL: phillips@hku.hk | - |
dc.identifier.doi | 10.1021/jo4008783 | - |
dc.identifier.pmid | 23672423 | - |
dc.identifier.scopus | eid_2-s2.0-84879287218 | - |
dc.identifier.hkuros | 220089 | - |
dc.identifier.volume | 78 | - |
dc.identifier.issue | 11 | - |
dc.identifier.spage | 5677 | - |
dc.identifier.epage | 5684 | - |
dc.identifier.isi | WOS:000320298700055 | - |
dc.publisher.place | United States | - |
dc.identifier.issnl | 0022-3263 | - |