Synthesis, electrochemical and photophysical properties of covalently linked porphyrin-polyoxometalates

Clémence Allain (1, 2, 3) , Delphine Schaming (2, 4) , N. Karakostas (2) , Marie Erard (2) , J. P. Gisselbrecht (5) , Sebastien Sorgues (2) , Isabelle Lampre (2) , L. Ruhlmann (2, 6) , B. Hasenknopf (7)

1 PPSM - Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires
2 LCPO - Laboratoire de Chimie Physique D'Orsay
3 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
4 ITODYS (UMR_7086) - Interfaces, Traitements, Organisation et Dynamique des Systèmes
5 Institut de Chimie de Strasbourg
6 Institut de Chimie de Strasbourg
7 IPCM - Institut Parisien de Chimie Moléculaire

Two covalently linked porphyrin-polyoxometalate hybrids have been prepared: an Anderson-type hexamolybdate [N(C(4)H(9))(4)](3)[MnMo(6)O(18){(OCH(2))(3)CNHCO(ZnTPP)}(2)] with two pendant zinc(ii)-tetraphenylporphyrins, and a Dawson-type vanadotungstate [N(C(4)H(9))(4)](5)H[P(2)V(3)W(15)O(59){(OCH(2))(3)CNHCO(ZnTPP)}] with one porphyrin. Electrochemical studies show independent redox processes for the organic and inorganic parts at usual potentials. Photophysical studies reveal an electron transfer from the excited porphyrin to the Dawson polyoxometalate, but not to the Anderson polyoxometalate. Time resolved absorption spectroscopy allows the identification of the electron transfer pathways and the determination of the time constants.

Mots clés: porphyrins; polyoxometalates

Domaines: Chimie inorganique; Chimie théorique et/ou physique

Clémence Allain, Delphine Schaming, N. Karakostas, Marie Erard, J. P. Gisselbrecht, et al.. Synthesis, electrochemical and photophysical properties of covalently linked porphyrin-polyoxometalates. Dalton Transactions, 2012, 42 (8), pp.2745-2754. ⟨10.1039/c2dt31415k⟩. ⟨hal-00796140⟩