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Photoinduced Proton Transfer Promoted by Peripheral Subunits for Some Hantzsch Esters

Lookup NU author(s): Dr Jerry Hagon, Emeritus Professor Anthony Harriman


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It is noted that, for a small series of 3,5-diacetyl-1,4-dihydrolutidine (DDL) derivatives and the corresponding Hantzsch esters, the presence of methyl groups at the 2,6-positions serves to extinguish fluorescence in solution but not in the solid state. Emission is weakly activated and affected by changes in solvent polarity. The latter situation arises because the optical transition involves intramolecular charge transfer. Calculations, both semiempirical and DFT, indicate that, in all cases, rotation of the carbonyl function is facile and that the dihydropyridine ring is planar. These calculations also indicate that the 2,6-methyl groups do not affect the generic structure of the molecule. It is proposed that illumination increases the molecular dipole moment and pushes electron density toward the carbonyl oxygen atom. Proton transfer can now occur from one of the methyl groups, leading to formation of a relatively low-energy, neutral intermediate, followed by a second proton transfer step that forms the enol. Reaction profiles computed for the ground-state species indicate that this route is highly favored relative to hydrogen transfer from the 4-position. The barriers for light-induced proton transfer are greatly reduced relative to the ground-state process but such large-scale structural transformations are hindered in the solid state. A rigid analogue that cannot form an enol is highly emissive in solution, supporting the conclusion that proton transfer is in competition to fluorescence in solution.

Publication metadata

Author(s): Azizi S, Ulrich G, Guglielmino M, le Calvé S, Hagon JP, Harriman A, Ziessel R

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry A

Year: 2015

Volume: 119

Issue: 1

Pages: 39-49

Print publication date: 08/01/2015

Online publication date: 04/12/2014

Acceptance date: 04/12/2014

ISSN (print): 1089-5639

ISSN (electronic): 1520-5215

Publisher: American Chemical Society


DOI: 10.1021/jp5078246


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Funder referenceFunder name
Newcastle University
A1106007OSEO through the project MINI FORMALAIR
ANR-11-ECOT-0013ANR through the project CAPFEIN