A Panchromatic Supramolecular Fullerene‐Based Donor–Acceptor Assembly Derived from a Peripherally Substituted Bodipy–Zinc Phthalocyanine Dyad

A panchromatic 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐ s‐ indacene –zinc phthalocyanine conjugate (Bodipy–ZnPc) 1 was synthesized starting from phthalocyanine aldehyde 4 , via dipyrromethane 3 and dipyrromethene 2 . Conjugate 1 represents the first example in which a Bodipy unit is tethered to the peripheral position of a phthalocyanine core. Electrochemical and optical measurements provided evidence for strong electronic interactions between the Bodipy and ZnPc constituents in the ground state of 1 . When conjugate 1 is subjected to photoexcitation in the spectral region corresponding to the Bodipy absorption, the strong fluorescence characteristic of the latter subunit is effectively quenched (i.e., ≥97 %). Excitation spectral analysis confirmed that the photoexcited Bodipy and the tethered ZnPc subunits interact and that intraconjugate singlet energy transfer occurs with an efficiency of ca. 25 %. Treatment of conjugate 1 with N ‐pyridylfulleropyrrolidine ( 8 ), an electron‐acceptor system containing a nitrogen ligand, gives rise to the novel electron donor–acceptor hybrid 1 ↔ 8 through ligation to the ZnPc center. Irradiation of the resulting supramolecular ensemble within the visible range leads to a charge‐separated Bodipy–ZnPc .+ –C 60 .− radical‐ion‐pair state, through a sequence of excited‐state and charge transfers, characterized by a remarkably long lifetime of 39.9 ns in toluene.