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Title: Distance‐Dependent Electron Transfer Kinetics in Axially Connected Silicon Phthalocyanine‐Fullerene Conjugates
Abstract

The effect of donor‐acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine‐C60dyads has been investigated. For this, two C60‐SiPc‐C60dyads,1and2, varying in their donor‐acceptor distance, have been newly synthesized and characterized. In the case of C60‐SiPc‐C601where the SiPc and C60are separated by a phenyl spacer, faster electron transfer was observed withkcsequal to 2.7×109 s−1in benzonitrile. However, in the case of C60‐SiPc‐C602, where SiPc and C60are separated by a biphenyl spacer, a slower electron transfer rate constant,kcs=9.1×108 s−1, was recorded. The addition of an extra phenyl spacer in2increased the donor‐acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of3SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high‐energy SiPc.+‐C60.−charge separated states (1.57 eV) populated the low‐lying3SiPc* (1.26 eV) prior returning to the ground state.

 
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NSF-PAR ID:
10237870
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
ChemPhysChem
Volume:
21
Issue:
20
ISSN:
1439-4235
Page Range / eLocation ID:
p. 2254-2262
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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