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Issue 7, 2015
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Steric shielding vs. σ–π orbital interactions in triplet–triplet energy transfer

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Abstract

The influence of non-covalent σ–π orbital interactions on triplet–triplet energy transfer (TTET) through tuning of the donor excitation energy remains basically unexplored. In the present work, we have investigated intermolecular TTET using donor moieties covalently linked to a rigid cholesterol (Ch) scaffold. For this purpose, diaryl ketones of π,π* electronic configuration tethered to α- or β-Ch were prepared from tiaprofenic acid (TPA) and suprofen (SUP). The obtained systems TPA-α-Ch, TPA-β-Ch, SUP-α-Ch and SUP-β-Ch were submitted to photophysical studies (laser flash photolysis and phosphorescence), in order to delineate the influence of steric shielding and σ–π orbital interactions on the rate of TTET to a series of energy acceptors. As a matter of fact, fine tuning of the donor triplet energy significantly modifies the rate constants of TTET in the absence of diffusion control. The experimental results are rationalized by means of theoretical calculations using first principles methods based on DFT as well as molecular dynamics.

Graphical abstract: Steric shielding vs. σ–π orbital interactions in triplet–triplet energy transfer

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Publication details

The article was received on 06 Mar 2015, accepted on 01 May 2015 and first published on 01 May 2015


Article type: Edge Article
DOI: 10.1039/C5SC00823A
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Citation: Chem. Sci., 2015,6, 4035-4041
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    Steric shielding vs. σ–π orbital interactions in triplet–triplet energy transfer

    I. Andreu, I. Morera, F. Palumbo, G. Sastre, F. Bosca and M. A. Miranda, Chem. Sci., 2015, 6, 4035
    DOI: 10.1039/C5SC00823A

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