A highly luminescent tetramer from a weakly emitting monomer: acid- and redox-controlled multiple complexation by
Giacomo Bergamini1, Andrea Fermi, Marianna Marchini
1Dipartimento di Chimica "G. Ciamician" and Interuniversity Center for the Chemical Conversion of Solar Energy (SolarChem), Università di Bologna, Via Selmi 2, 40126 Bologna (Italy), Fax: (+39) 051-2099456.
Abstract:
The tetrahedral, shape-persistent molecule 1(4+), containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm(-1)) and a very strong fluorescence (Φem = 40 %), compared with the monomer 2(+) (Φem = 0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1(4+) and 2(+) show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.
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