Details

Autor(en) / Beteiligte

• Chahal, Mandeep K
• Gobeze, Habtom B
• Webre, Whitney A
• Karr, Paul A
• Payne, Daniel T
• Ariga, Katsuhiko
• D'Souza, Francis
• Hill, Jonathan P

Titel

Electron and energy transfer in a porphyrin-oxoporphyrinogen-fullerene triad, ZnP-OxP-C

Ist Teil von

• Physical chemistry chemical physics : PCCP, 2020-07, Vol.22 (25), p.14356-14363

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A multichromophoric triad, ZnP-OxP-C 60 containing porphyrin ( ZnTPP hereafter ZnP ), oxoporphyrinogen ( OxP ) and fullerene ( C 60 ) has been synthesized to probe the intramolecular dynamics of its electron and energy transfer in relation to the presence of the closely linked electron deficient OxP-C 60 'special pair', constructed as a mimic of the naturally occurring photosynthetic antenna-reaction center. The DFT optimized structure of the triad reveals the relative spatial remoteness of the ZnP entity with proximal OxP / C 60 entities. Free-energetics of different energy and electron transfer events were estimated using spectral, computational and electrochemical studies, according to the Rehm-Weller approach. Femtosecond transient absorption spectral studies revealed energy transfer from 1 ZnP* to OxP to yield ZnP- 1 OxP*-C 60 , and electron transfer to yield ZnP&z.rad; + -OxP-C 60 &z.rad; − and/or ZnP-OxP&z.rad; + -C 60 &z.rad; − charge seperated states. That is, the ZnP entity in the triad operates as both antenna and electron donor to generate relatively long-lived charge separated states thus mimicking the early photoevents of natural photosynthesis. Competitive energy and electron transfer in a newly synthesized supramolecular triad composed of zinc porphyrin, oxoporphyrinogen and C 60 has been demonstrated using ultrafast pump-probe spectroscopy.