Heteroleptic Ruthenium Sensitizers That Contain an Ancillary Bipyridine Ligand Tethered with Hydrocarbon Chains for Efficient Dye‐Sensitized Solar Cells

New heteroleptic ruthenium complexes have been synthesized and used as the sensitizers for dye-sensitized solar cells (DSSCs). The ancillary bipyridine ligand contains rigid aromatic segments (fluorene-, carbazole-, or dithieno[3,2-b:2′,3′-d]pyrrole-substituted bipyridine) tethered with a hydrophobic hexyl substituent. The conjugated aromatic segment results in significant bathochromic shift and hyperchromic effects in these complexes compared with Z907 (cis-[RuLL′(NCS)2]; L=4,4′-dicarboxylic acid-2,2′-bipyridine, L′=4,4′-dinonyl-2,2′- bipyridine). The long hydrocarbon chains help to suppress the dark current if appropriately disposed. DSSCs that use these complexes exhibit very impressive conversion efficiencies (5.94 to 6.91 %) that surpass that of Z907-based (6.36 %) DSSCs and are comparable with that of N719-based standard cells (7.13 %; N719=cis-di(thiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)ruthenium(II) bis(tetrabutylammonium)) fabricated and measured under similar conditions (active area: 0.5×0.5 cm2; AM 1.5 sunlight).