Cyclometalated Pt complex based random terpolymers as electron acceptors for all polymer solar cells

Various molar ratios of platinum complexes were introduced into the conjugated backbone of the well‐studied poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)](PNDIT2) acceptor polymer through random terpolymer approach. Terpolymers PNDIT2Ptx (x = 1, 2 and 5) exhibited slightly higher melting point (T_m), crystallization temperature, HOMO and LUMO energy levels than the control PNDIT2 copolymer due to the introduction of small amount of weaker electron‐withdrawing bulky rigid Pt complex instead of strong electron‐withdrawing flexible naphthalene diimide. When blended them with poly[[2,6′‐4,8‐di(5‐ethylhexylthienyl)benzo[1,2‐b;3,3‐b] dithiophene] [3‐fluoro‐2[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7‐Th) in all polymer solar cells, enhanced power conversion efficiency of 4.51% (3.74%) was obtained in terpolymer PNDIT2Pt1 based device compared to 3.88% (3.24%) of the control PNDIT2 at the same inverted (conventional) device conditions. The enhancement was probably ascribed to higher hole and electron transport ability and more efficient charge separation. To the best of our knowledge, this is the first example of random terpolymer acceptors based on heavy metal complexes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 105–115