Title: Photoannealing of Merocyanine Aggregates

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
ORCiD logo [1];  [1]; ORCiD logo [1];  [2];  [3];  [2]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [5]
  1. Friedrich Schiller Univ. Jena, Jena (Germany); Leibniz Institute of Photonic Technology Jena (IPHT), Jena (Germany)
  2. Friedrich Schiller Univ. Jena, Jena (Germany)
  3. Leibniz Institute of Photonic Technology Jena (IPHT), Jena (Germany)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States); Friedrich Schiller Univ. Jena, Jena (Germany)
  5. Friedrich Schiller Univ. Jena, Jena (Germany); Leibniz Institute of Photonic Technology Jena (IPHT), Jena (Germany); sciclus GmbH & Co. KG, Jena (Germany)
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In this study we elucidate the fundamental difference between aggregate formation of donor–π–acceptor merocyanines in their electronic ground and excited states. While increasing the π-bridge size favors formation of π-stacked aggregates in the dark, irradiation with visible light causes reorientation of the dyes to form prototype H-aggregates with compensating dipole moments. This photoannealing changes the supramolecular structure and its UV–vis spectroscopic properties dramatically, thus being of importance for the function of active layers composed of these dyes. Aggregates of the ground state dyes are bound cooperatively through ππ-London dispersion interactions and hydrogen bonds between the polar α-cyano-carboxylic acid groups. However, charge transfer upon photoexcitation leads to repulsion of the polar acid groups. Electronic excitation of the dyes approximately doubles the ground state dipole moment, thus driving molecular reorientation into prototype H-aggregate structures. We show that this photoinduced supramolecular rearrangement can disrupt the large polymeric aggregates formed in the dark. The photoinduced supramolecular structural changes reported in this work will influence the performance of optoelectronic devices composed of these structures and must be controlled to avoid morphological decomposition of active layers upon operation.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1493575
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 51 Vol. 122; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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