Ultrafast photoinduced energy and electron transfer in multi-modular donor-acceptor conjugates

New multi-modular donor-acceptor conjugates featuring zinc porphyrin (ZnP), catechol-chelated boron dipyrrin (BDP), triphenylamine (TPA) and fullerene (C ₆₀), or naphthalenediimide (NDI) have been newly designed and synthesized as photosynthetic antenna and reaction-center mimics. The X-ray structure of triphenylamine-BDP is also reported. The wide-band capturing polyad revealed ultrafast energy-transfer (k _ENT=1.0×10 ¹² s ^-1) from the singlet excited BDP to the covalently linked ZnP owing to close proximity and favorable orientation of the entities. Introducing either fullerene or naphthalenediimide electron acceptors to the TPA-BDP-ZnP triad through metal-ligand axial coordination resulted in electron donor-acceptor polyads whose structures were revealed by spectroscopic, electrochemical and computational studies. Excitation of the electron donor, zinc porphyrin resulted in rapid electron-transfer to coordinated fullerene or naphthalenediimide yielding charge separated ion-pair species. The measured electron transfer rate constants from femtosecond transient spectral technique in non-polar toluene were in the range of 5.0×10 ⁹-3.5×10 ¹⁰ s ^-1. Stabilization of the charge-separated state in these multi-modular donor-acceptor polyads is also observed to certain level.