Starburst-Shaped D-π-A Chromophores Possessing a Hexaethynylbenzene Core for Dye-Sensitized Solar Cells.

Two starburst-shaped organic chromophores, incorporating a hexaethynylbenzene core modified by five donor branches (D-branches) of (p-dioctylaminostyryl)benzene and one acceptor/anchoring branch (A-branch) of either carboxylic acid-terminated phenylethynylbenzene (SB-07) or cyanoacrylic acid-terminated diketopyrrolopyrrole (DPP)-thiophene (SB-08), were synthesized and applied to dye-sensitized solar cells (DSSCs). In these chromophores, the common donor moiety, five (p-dioctylaminostyryl)phenyl groups, exhibits excellent optical absorption in the visible region (molar absorption coefficient ε > 105 M-1 cm-1 below 500 nm). The A-branch of SB-07 does not possess strong electron-accepting properties; however, the A-branch of SB-08, the DPP-thiophene moiety, serves as a strong electron acceptor site. Furthermore, the intramolecular charge-transfer (ICT) transition between the thiophene and DPP moieties extends the optical absorption range to the near-infrared region (∼800 nm). Optimized DSSC devices using SB-08 with coadsorption of chenodeoxycholic acid, in conjunction with iodide/triiodide-based electrolytes, exhibited incident photon-to-current conversion efficiency (IPCE) exceeding 70% in the 370-700 nm range and over 20% even at 800 nm, with a short-circuit photocurrent density (Jsc) of 19.3 mA cm-2 and a power conversion efficiency (PCE) of 6.4% under AM 1.5G illumination (100 mW cm-2). These results are considerably better than those of SB-07 (Jsc = 7.0 mA cm-2, PCE = 3.3%). The starburst-shaped architecture presented here can be used as a novel structural motif for metal-free organic sensitizers because it enables flexible modification of the multiple D-branches that enhance light-harvesting ability and the A-branch that serves as an excited electron transport pathway.