TY - JOUR
T1 - Photoinduced Electron and Energy Transfer in a Molecular Triad Featuring a Fullerene Redox Mediator
AU - Antoniuk-Pablant, Antaeres
AU - Kodis, Gerdenis
AU - Moore, Ana
AU - Moore, Thomas
AU - Gust, Devens
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/7/14
Y1 - 2016/7/14
N2 - In order to investigate the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C60) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CYP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CYP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of 1P-C60-CYP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CYP. The P•+-C60•--CYP charge-separated state transfers an electron to CYP to produce a final P•+-C60-CYP•- state. The same state is formed from P-C60-1CYP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediate P•+-C60•--CYP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. This is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.
AB - In order to investigate the possibility of a fullerene acting as an electron and/or singlet energy relay between a donor chromophore and an acceptor, a triad consisting of a fullerene (C60) covalently linked to both a porphyrin energy and electron donor (P) and a β-tetracyanoporphyrin energy and electron acceptor (CYP) was synthesized. Steady state and time-resolved spectroscopic investigations show that the porphyrin first excited singlet state donates singlet excitation and an electron to the fullerene and also donates singlet excitation to the CYP. All three processes differ in rate constant by factors of ≤1.3, and all are much faster than the decay of 1P-C60-CYP by unichromophoric processes. The fullerene excited state accepts an electron from P and donates singlet excitation energy to CYP. The P•+-C60•--CYP charge-separated state transfers an electron to CYP to produce a final P•+-C60-CYP•- state. The same state is formed from P-C60-1CYP. Overall, the final charge-separated state is formed with a quantum yield of 85% in benzonitrile, and has a lifetime of 350 ps. Rate constants for formation and quantum yields of all intermediate states were estimated from results for the triad and several model compounds. Interestingly, the intermediate P•+-C60•--CYP charge-separated state has a lifetime of 660 ps. It is longer lived than the final state in spite of stronger coupling of the radical ions. This is ascribed to the fact that recombination lies far into the inverted region of the Marcus rate constant vs thermodynamic driving force relationship.
UR - http://www.scopus.com/inward/record.url?scp=84978698470&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84978698470&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.6b03470
DO - 10.1021/acs.jpcb.6b03470
M3 - Article
AN - SCOPUS:84978698470
SN - 1520-6106
VL - 120
SP - 6687
EP - 6697
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 27
ER -