We present the tunability of the photophysical and electrochemical properties of a series of intramolecular charge transfer compounds by facile molecular design and synthesis. The photovoltaic performances based on these sublimable materials and C(60) bulk heterojunction cells are compared and reported. The structural modification of the charge transfer dyes altered not only the electronic properties, but also the morphology of the bulk heterojunction thin films, as revealed by AFM and SEM studies. Addition of PEDOT:PSS between the ITO and the photoactive layer improved the hole injection from the photosensitizer into the anode, and the overall power conversion efficiency is also enhanced.

a b s t r a c tA series of sublimable substituted chlorotricarbonyl bis(phenylimino)acenaphthene rhenium(I) complexes was synthesized and used in the fabrication of photovoltaic devices. The hole and electron carrier mobilities of these complexes are in the order of 10 À3 to 10 À4 cm 2 V À1 s À1 . Heterojunction devices with CuPc/complex/C 60 (CuPc = copper phthalocyanine) as the active layer and bulk heterojunction devices with complex:C 60 as the active layer were fabricated. The rhenium complexes function as photosensitizer in the devices, and exhibit optical absorption in the region between 500 and 550 nm within which other components in the device do not absorb. Other devices with hole transport materials, exciton blocking materials, and different active layer thickness were also fabricated. Variation of substitution groups in the ligand did not show significant difference in device performance. The best power conversion efficiency of the devices was measured to be 1.29% under illumination of AM1.5 simulated solar light.

Conjugated copolymers with novel low bandgap rhenium(I) complexes on the polymer main-chain are reported. The low bandgap metal-containing polymers were synthesized by Suzuki cross-coupling polycondensation or Stille coupling polymerization. The metal free copolymers are conjugatively-linked with functionalized intramolecular charge transfer units, which exhibited prominent absorption band in the UV-vis region. These functionalized charge transfer units not only broadened the absorption spectrum, but also functioned as a bidentate ligand. Upon the complexation of rhenium(I) pentacarbonyl chloride, the absorption spectrum of the resulting polymers was further boardened, and the bandgap was reduced. The material design of this work has opened up a new approach in developing low bandgap metal-containing polymers as light harvesting materials.

Low‐bandgap rhenium(I) complex with absorption onset at 795 nm in solution was tethered onto π‐conjugated polymer. The conjugated copolymer provides solution processability of the metallopolymer, and the pendant allows the low energy‐absorbing Re(I) complex units to be evenly distributed on the thin film. The copolymer tethered with low‐bandgap rhenium complex was synthesized by Suzuki cross‐coupling reaction. The metal‐free polymer (poly‐1) tethered with functionalized intramolecular charge transfer dye, 2‐phenyl‐3‐pyridin‐2‐yl‐5,7‐di‐2‐thienylthieno[3,4‐b]pyrazine, exhibited high molecular weight, good film‐forming properties, and excellent solution processability. The pendants of the conjugated polymer possess donor–acceptor characters and broaden the absorption band. These pendants can function as bidentate ligands for metal chelation. The solubilizing groups on the monomers provide good solubility to the polymer even with high content of metal chelation. Upon the complexation with rhenium(I) pentacarbonyl chloride, the absorption spectrum of the resulting metallopolymer was further extended toward the near‐infrared region. Photovoltaic performances based on this metallopolymer have been studied. The design approach of these metallopolymers provides synthetic feasibility for coordinating wide range of metal ions on the pendant, and the resulting low‐bandgap polymer can be a potential candidate for light harvesting material in solar cell applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2311–2319, 2010