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Article Dans Une Revue Inorganic Chemistry Frontiers Année : 2021

Acid-triggering of light-induced charge-separation in hybrid organic/inorganic molecular photoactive dyads for harnessing solar energy

Elisabetta Benazzi
Joshua Karlsson
  • Fonction : Auteur
Youssef Ben M'Barek
  • Fonction : Auteur
Pavel Chabera
  • Fonction : Auteur
Sébastien Blanchard
Sandra Alves
Anna Proust
Tönu Pullerits
  • Fonction : Auteur
  • PersonId : 1088320
Guillaume Izzet
Elizabeth A Gibson
  • Fonction : Auteur
  • PersonId : 1090123

Résumé

H + modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described. The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates (POMs, where K M = [PM 11 O 39 ] and M = Mo or W) covalently grafted via an organotin linker to a bodipy (BOD) photosensitizer. The relative potentials of the photosensitizer and POM are aligned such that lightinduced electron transfer from BOD to POM is permitted for the polyoxomolybdate K Mo Sn [BOD] but not effective for the polyoxotungstate analogue K W Sn [BOD]. In both cases, the addition of acid shifts the redox potential of the POM only, to increase the driving force for electron transfer. This leads to chargeseparation being switched on for K W Sn [BOD] in the presence of acid. The addition of acid to K Mo Sn [BOD] accelerates charge-separation by an order of magnitude (from 2 ns to 200 ps) and is accompanied by a deceleration of charge recombination, leading to a charge-separated state lifetime of up to 1.3 µs. This behaviour is consistent with proton coupled electron transfer, which has previously been observed electrochemically for POMs, but this study shows, for the first time, the impact of protonation on photoinduced electron transfers.
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Dates et versions

hal-03130031 , version 1 (03-02-2021)

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Elisabetta Benazzi, Joshua Karlsson, Youssef Ben M'Barek, Pavel Chabera, Sébastien Blanchard, et al.. Acid-triggering of light-induced charge-separation in hybrid organic/inorganic molecular photoactive dyads for harnessing solar energy. Inorganic Chemistry Frontiers, 2021, ⟨10.1039/d0qi01368d⟩. ⟨hal-03130031⟩
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