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- Title
The Role of Torsional Dynamics on Hole and Exciton Stabilization in π‐Stacked Assemblies: Design of Rigid Torsionomers of a Cofacial Bifluorene.
- Authors
Wang, Denan; Ivanov, Maxim V.; Kokkin, Damian; Loman, John; Cai, Jin‐Zhe; Reid, Scott A.; Rathore, Rajendra
- Abstract
Abstract: Exciton and charge delocalization across π‐stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene (F2) torsionomers were designed, synthesized, and characterized: unhindered (model) MeF2, sterically hindered tBuF2, and cyclophane‐like CF2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich‐like arrangement, as seen by strong excimeric‐like emission only in CF2 and MeF2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered tBuF2, as judged by 160 mV hole stabilization and a near‐IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π‐stacked assemblies.
- Subjects
DELOCALIZATION energy; FLUORENE; METHANE; CHLORFLURENOL; POLYMERS
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 27, p8321
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201804337