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Unexpected Drastic Decrease in the Excited‐State Electronic Communication between Porphyrin Chromophores Covalently Linked by a Palladium(II) Bridge

2014; Wiley; Volume: 20; Issue: 40 Linguagem: Inglês

10.1002/chem.201403146

1521-3765

Mohammed Abdelhameed, Paul‐Ludovic Karsenti, Adam Langlois, Jean‐François Lefebvre, Sébastien Richeter, Romain Ruppert, Pierre D. Harvey,

Organic Light-Emitting Diodes Research

Abstract A dyad built up of a zinc(II) porphyrin and the corresponding free base, [Zn‐Fb] , fused to N‐heterocyclic carbene (NHCs) ligands, respectively acting as singlet energy donor and acceptor, and a bridging trans ‐PdI 2 unit, along with the corresponding [Zn‐Zn] and [Fb‐Fb] dimers were prepared and investigated by absorption and emission spectroscopy and density functional computations. Despite favorable structural and spectroscopic parameters, unexpectedly slow singlet energy transfer rates are measured in comparison with the predicted values by the Förster theory and those observed for other structurally related dyads. This observation is rationalized by the lack of large molecular orbital (MO) overlaps between the frontier MOs of the donor and acceptor, thus preventing a double electron exchange through the trans ‐PdI 2 bridge, and by an electronic shielding induced by the presence of this same linker preventing the two chromophores to fully interact via their transition dipoles.