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Journal of Chemical Physics, Vol.115, No.20, 9601-9606, 2001
S-1 similar to > T-1 intersystem crossing in pi-conjugated organic polymers
Quantum yields for triplet formation have been determined for seven common pi -conjugated polymers in benzene solution using time-resolved photoacoustic calorimetry (PAC) in conjunction with fluorescence quantum yields, singlet and triplet energies. The polymers studied include three poly(thiophenes), poly(2-methoxy,5-(2'-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV), a cyano derivative of MEH-PPV, a ladder type poly(p-phenylene) (MeLPPP), and a poly(fluorene). Yields of singlet oxygen formation have also been determined for these polymers in benzene by time-resolved phosphorimetry, and are in reasonable agreement with triplet yields obtained by PAC. Polythiophenes show the highest intersystem crossing yields, which are suggested to result from extensive spin-orbit coupling. Where singlet oxygen yields are less than triplet yields, it is suggested that interaction of molecular oxygen with the ground state of the polymers may be involved.