Document Type
Journal Article
Department/Unit
Department of Chemistry
Title
Synthesis and photovoltaic properties of new metalloporphyrin-containing polyplatinyne polymers
Language
English
Abstract
Three new solution-processable platinum(II) polyyne polymers containing zinc(II) porphyrinate chromophores P1, P2, and P3 and their corresponding dinuclear model complexes were synthesized via the CuI-catalyzed dehydrohalogenation reaction of the platinum(II) chloride precursor and each of the respective bis(ethynyl)-zinc(porphyrin) metalloligands. The thermal, photophysical (absorption, excitation and emission spectra), electrochemical, and photovoltaic properties of P1-P3 were investigated. These results are also correlated by time-dependent density functional theory (TDDFT) calculations. The computations corroborate the presence of moderate conjugation in the π-systems, somewhat more accentuated for P3 where more favorable dihedral angles between the porphyrin and thiophene rings are noted. Moreover, the computed excited states are predicted to be π-π* in nature with some charge transfer components from the trans-[-C≡CPt(L)2C≡ C-]n unit to the porphyrin rings. The optical bandgaps range from 1.93 to 2.02 eV for P1-P3. Intense π-π*-localized fluorescence emissions typical of the Q-bands of the polymers were observed. The effect of thiophene ring along the polymer chain on the extent of π-conjugation, luminescent and photovoltaic properties of these metalated materials was also examined. Bulk heterojunction solar cells using these metallopolymers as an electron donor blended with a methanofullerene electron acceptor were studied. In one case, the metallopolymer P3 showed a power conversion efficiency of 1.04% with the open-circuit voltage of 0.77 V, short-circuit current density of 3.42 mA cm-2 and fill factor of 0.39 under illumination of an AM 1.5 solar cell simulator. © 2011 American Chemical Society.
Publication Date
2011
Source Publication Title
Macromolecules
Volume
44
Issue
13
Start Page
5155
End Page
5167
Publisher
American Chemical Society
DOI
10.1021/ma2006206
Link to Publisher's Edition
ISSN (print)
00249297
ISSN (electronic)
15205835
Recommended Citation
Zhan, Hongmei, Simon Lamare, Annie Ng, Tommy Kenny, Hannah Guernon, Wai-Kin Chan, Aleksandra B. Djurišić, Pierre D. Harvey, and Wai-Yeung Wong. "Synthesis and photovoltaic properties of new metalloporphyrin-containing polyplatinyne polymers." Macromolecules 44.13 (2011): 5155-5167.