期刊
INORGANIC CHEMISTRY
卷 56, 期 5, 页码 2506-2517出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b02684
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资金
- Natural Sciences and Engineering Research Council of Canada
- Fonds de recherche du Quebec Nature et technologies
- Centre Quebecois des Materiaux Fonctionnels
- Centre d'Etudes des Materiaux Optiques et Photoniques de l'Universite de Sherbrooke
- Agence National de la Recherche
The demetalation of a precursor dyad, 3, built upon a zinc(II)-containing artificial special pair and free-base antenna, leads to a new dyad, 4, for singlet energy transfer composed of cofacial free-base porphyrins (acceptor), [Fb](2) bridged by a 1,4-C6H4 group to a free-base antenna (donor), [Fb]. This dyad exhibits the general structure [M](2)-C6H4-[Fb], where [M](2) = [Fh](2), and completes a series reported earlier, where [M](2) = [Mg](2) (2) and [Zn](2) (3). The latter dyads exhibit a bidirectional energy-transfer process at 298 K for 2 and at 77 K for 3. Interestingly, a very scarce case of cycling process is observed for the zinc-containing dyad at 298 K. The newly reported compound 4 exhibits a quasi unidirectional process [Fb]*->[Fb](2), (major, k(ET) = 2 X 10(11) s(-1) at 298 K), where the remaining is [Fb](2)*->[Fb] (minor, k(ET) = 8 X 10(9) s(-1) at 298 K), thus completing all possibilities. The results are analyzed in terms of molecular orbital couplings (density functional theory computations), Forster resonance energy transfer parameters, and temperature dependence of the decay traces. This study brings major insights about artificial special pair-containing dyads and clearly contributes to a better understanding of the communication between the two main components of our models and those already described in the literature.
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