6533b82afe1ef96bd128c37a

RESEARCH PRODUCT

Energy transfers in monomers, dimers, and trimers of zinc(II) and palladium(II) porphyrins bridged by rigid Pt-containing conjugated organometallic spacers

Diana BellowsRoger GuilardMaya El OjaimiJean-michel BarbePierre D. HarveyClaude P. GrosShawkat M. Aly

subject

Models MolecularTime FactorsOrganoplatinum CompoundsStereochemistryMetalloporphyrinsMolecular Conformationchemistry.chemical_elementZincConjugated system010402 general chemistryLigands01 natural sciences7. Clean energyAbsorptionInorganic Chemistrychemistry.chemical_compoundAtomtrimerPhysical and Theoretical ChemistryComputingMilieux_MISCELLANEOUSmetalloporphyrinenergy transfer010405 organic chemistrySpectrum AnalysiszincmonomerdimerpalladiumPorphyrin0104 chemical sciences3. Good health[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistryCrystallographyMonomerchemistryAbsorption bandLuminescent Measurements[ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistryconjugated organometallic spacerDimerizationExcitationPalladium

description

A series of linear monomers (spacer-M(P)), dimers (M(P)-spacer-M'(P)), and trimers (M(P)-spacer-M'(P)-spacer-M(P)) of spacer/metalloporphyrin systems (M' = Zn, M = Zn, Pd, P = porphyrin, and spacer = trans-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- (L = PEt(3))) including mixed metalloporphyrin compounds, were synthesized and characterized. The S(1) and T(1) energy transfers Pd(P)*--Zn(P) occur with rates of approximately 2 x 10(9) s(-1), S(1), and 0.15 x 10(3) (slow component) and 4.3 x 10(3) s(-1) (fast component), T(1). On the basis of a literature comparison with a related dyad, the Pt atom in the conjugated chain slows down the transfers. The excitation in the absorption band of the trans-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- spacer in the 300-360 nm range also leads to T(1) energy transfer (spacer* --M(P); M = Zn, Pd) with rates of 10(4) s(-1).

https://hal.archives-ouvertes.fr/hal-00458419