Intersystem Crossing Processes in Non-Planar Aromatic Heterocyclic Molecules

[en] A comprehensive study of the photophysical properties of a series of monoaza[5]helicenes is presented on the basis of joint optical spectroscopy and quantum chemistry investigations. The molecules have been characterized by absorption and CW/time-resolved luminescence measurements. All quantities related to spin-orbit-coupling processes, such as intersystem crossing rates and radiative phosphorescence lifetimes, were found to depend strongly on the nitrogen position within the carbon backbone. Density functional theory and semiempirical quantum-chemical methods were used to evaluate the molecular geometries, the characteristics of the excited singlet and triplet states, and the spin-orbit coupling matrix elements. We demonstrate that the magnitude of spin-orbit coupling is directly correlated with the degree of deviation from planarity. The trends from the calculated photophysical quantities, namely, radiative fluorescence and phosphorescence decay rates and intersystem crossing rates, of the mono-aza-helicenes are fully consistent with experiment.

Disciplines :

Chemistry
Physics

Author, co-author :

Schmidt, K.

Brovelli, S.

Coropceanu, V.

Beljonne, David ; Université de Mons > Faculté de Médecine et de Pharmacie > Chimie générale, organique et biomédicale ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux

Cornil, Jérôme ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux

Bazzini, C.

Caronna, T.

Tubino, R.

Meinardi, F.

Shuai, Z.

Brédas, Jean-Luc ; Université de Mons > Faculté des Sciences > Chimie des matériaux nouveaux

Language :

English

Title :

Intersystem Crossing Processes in Non-Planar Aromatic Heterocyclic Molecules

Publication date :

25 October 2007

Journal title :

Journal of Physical Chemistry. A

ISSN :

1089-5639

Publisher :

American Chemical Society, Washington, United States - District of Columbia

Volume :

111

Issue :

Pages :

10490-10499

Peer reviewed :

Peer Reviewed verified by ORBi

Research unit :

S817 - Chimie des matériaux nouveaux

Research institute :

R400 - Institut de Recherche en Science et Ingénierie des Matériaux

Commentary :

Publié en ligne le 2 octobre 2007

Available on ORBi UMONS :

since 10 June 2010

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Scopus citations^®

257

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253

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189

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