http://dx.doi.org/10.1021/ma2006206">
 

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

ISSN (print)

00249297

ISSN (electronic)

15205835

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