Isomeric Fluorene-based Heteroundecenes with Different Side Chains Anchoring Positions for Small Molecule Acceptors

Two isomeric fluorene-based heteroundecenes of bis(thienocyclopenthieno[3,2-b]thieno)fluorene(BT2T-F)and bis(dithieno[3,2-b:2’,3’-d]thiophene)cyclopentafluorene(B3T-F)have been designed and synthesized.The side chains of 4-hexylphenyl anchor on the 5th and 8th positions in B3T-F while on the 4th and 9th positions in BT2T-F,in which the former is closer to the center of the fused ring.The corresponding acceptor-donor-acceptor(A-D-A)type small molecule acceptors(SMAs)of BT2T-FIC and B3T-FIC were prepared by linking BT2T-F and B3T-F as fused ring donor units with the acceptor unit of 2-(5,6-difluoro-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC-2F),respectively.B3T-FIC presents a superior crystallinity with intense face-on π-π stacking in its neat film while BT2T-FIC is more disordered.When blended with PBDB-T-2Cl as a polymer donor,the optimized PBDB-T-2Cl:BT2T-FIC device exhibits an averaged power conversion efficiency(PCE)of 10.56%while only 7.53%in the PBDB-T-2Cl:B3T-FIC device.The improved short-circuit current(J_(sc))and fill factor(FF)of the PBDB-T-2Cl:BT2T-FIC device are the main contribution of its higher performance,which is attributed to its more efficient and balanced charge transport and better carrier recombination suppression.Given that BT2T-FIC blend and B3T-FIC blend films both take a preferential face-on orientatedπ-πstacking with comparable distances,the suitable SMA domain size obtained in the BT2T-FIC blend could account for its more efficient photovoltaic performance.These results highlight the importance of side-chain strategy in developing efficient SMAs with huge fused ring cores.