4.8 Article

Aggregation-Induced Photon Upconversion through Control of the Triplet Energy Landscapes of the Solution and Solid States

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 26, Pages 7544-7549

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201501449

Keywords

aggregation; donor-acceptor systems; photochemistry; photon upconversion; triplet-triplet annihilation

Funding

  1. Ministry of Education, Culture Sports, Science and Technology of Japan [25220805, 25410030, 26104529]
  2. Noguchi Institute, Morino Foundation for Molecular Science
  3. JSPS-NSF International Collaborations in Chemistry (ICC) program
  4. Grants-in-Aid for Scientific Research [26104529, 26104538, 25410030] Funding Source: KAKEN

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Aggregation-induced photon upconversion (iPUC) based on control of the triplet energy landscape is demonstrated for the first time. When a triplet state of a cyano-substituted 1,4-distyrylbenzene derivative is sensitized in solution, no upconverted emission based on triplet-triplet annihilation (TTA) was observed. In stark contrast, crystalline solids obtained by drying the solution revealed clear upconverted emission. Theoretical studies unveiled an underlying switching mechanism: the excited triplets in solution immediately decay back to the ground state through conformational twisting around a CC bond and photoisomerization, whereas this deactivation path is effectively inhibited in the solid state. The finding of iPUC phenomena highlights the importance of controlling excited energy landscapes in condensed molecular systems.

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