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Title: Triplet-State and Singlet Oxygen Formation in Fluorene-Based Alternating Copolymers
Authors: Fonseca, S. M. 
Pina, J. 
Arnaut, L. G. 
Melo, J. Seixas de 
Burrows, H. D. 
Chattopadhyay, N. 
Alcácer, L. 
Charas, A. 
Morgado, J. 
Issue Date: 27-Apr-2006
Publisher: American Chemical Society
Citation: The Journal of Physical Chemistry B. 110:16 (2006) 8278-8283.
Abstract: Data are reported on the triplet states of a series of fluorene-based A-alt-B type alternating copolymers based on pulse radiolysis-energy transfer and flash photolysis experiments. From the pulse radiolysis experiments, spectra are given for eight copolymers involving phenylene, thiophene, benzothiadiazole, and oligothienylenevinylene groups. Quantum yields for triplet-state formation (ΦT) have been obtained by flash photolysis following laser excitation and in one case by photoacoustic calorimetry. In addition, yields of sensitized formation of singlet oxygen have been determined by time-resolved phosphorescence and are, in general, in excellent agreement with the ΦT values. In all cases, the presence of thiophene units is seen to increase intersystem-crossing quantum yields, probably because of the presence of the heavy sulfur atom. However, with the poly[2,7-(9,9-bis(2‘-ethylhexyl)fluorene)-alt-1,4-phenylene] (PFP), thiophene S,S-dioxide (PFTSO2) and benzothiadiazole (F8BT) copolymers, low yields of triplet formation are observed. With three of the copolymers, the energies of the triplet states have been determined. With PFP, the triplet energy is virtually identical to that of poly[2,7-(9,9-bis(2‘-ethylhexyl)fluorene)]. In contrast, with fluorene−thiophene copolymers PFaT and PF3T, the triplet energies are closer to those of thiophene oligomers, indicating that there is significant conjugation between fluorene and thiophene units but also that there is a more localized triplet state than with the homopolymers.
ISSN: 1520-6106
DOI: 10.1021/jp060251f
Rights: openAccess
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais

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