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Cyclobutadiene–C60 Adducts: N-Type Materials for Organic Photovoltaic Cells with High VOC



New tetraalkylcyclobutadiene–C60 adducts are developed via Diels–Alder cycloaddition of C60 with in situ generated cyclobutadienes. The cofacial π-orbital interactions between the fullerene orbitals and the cyclobutene are shown to decrease the electron affinity and thereby increase the lowest unoccupied molecular orbital (LUMO) energy level of C60 significantly (ca. 100 and 300 meV for mono- and bisadducts, respectively). These variations in LUMO levels of fullerene can be used to generate higher open-circuit voltages (VOC) in bulk heterojunction polymer solar cells. The tetramethylcyclobutadiene–C60 monoadduct displays an open-circuit voltage (0.61 V) and a power conversion efficiency (2.49%) comparable to the widely used P3HT/PCBM (poly(3-hexylthiophene/([6,6]-phenyl-C61-butyric acid methyl ester) composite (0.58 V and 2.57%, respectively). The role of the cofacial π-orbital interactions between C60 and the attached cyclobutene group was probed chemically by epoxidation of the cyclobutene moiety and theoretically through density functional theory calculations. The electrochemical, photophysical, and thermal properties of the newly synthesized fullerene derivatives support the proposed effect of functionalization on electron affinities and photovoltaic performance.