title: Unexpected drastic decrease in the excited-state electronic communication between porphyrin chromophores covalently linked by a palladium(II) bridge.
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-PdI2 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-PdI2 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.
authors.affiliation: Département de Chimie, Université de Sherbrooke, Sherbrooke, PQ, J1K 2R1 (Canada).
authors.forename: Mohammed
authors.initials: M
authors.lastname: Abdelhameed
authors.forename: Paul-Ludovic
authors.initials: PL
authors.lastname: Karsenti
authors.forename: Adam
authors.initials: A
authors.lastname: Langlois
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Lefebvre
authors.forename: Sébastien
authors.initials: S
authors.lastname: Richeter
authors.forename: Romain
authors.initials: R
authors.lastname: Ruppert
authors.forename: Pierre D
authors.initials: PD
authors.lastname: Harvey
mesh_terms: D004583:Electrons; D004735:Energy Transfer; D006571:Heterocyclic Compounds / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D008958:Models, Molecular; D010165:Palladium / Q000737:chemistry*; D011789:Quantum Theory; D015032:Zinc / Q000737:chemistry*
chemical_list: D006571:Heterocyclic Compounds; D008665:Metalloporphyrins; C030011:carbene; D010165:Palladium; D015032:Zinc; D008697:Methane
keywords: Förster theory; carbenes; palladium; porphyrins; singlet energy transfer