Energy transfer in supramolecular calix[4]arene—Perylene bisimide dye light harvesting building blocks: Resolving loss processes with simultaneous target analysis

By the application of simultaneous target analysis of multiple femtosecond transient absorption data sets we have identified two loss channels within multi-chromophoric light harvesting arrays. Perylene bisimide-calix[4]arene arrays composed of up to three different types of perylene bisimide (PBI) chromophores, orange (o), red (r), and green (g) PBIs (named after their colors as solids), have previously been studied by transient absorption spectroscopy (Hippius et al., J. Phys. Chem C 112:2476, 2008) and here we present a simultaneous target analysis of those data matrices. A covalent system containing the red chromophore (r) and calix[4]arene (c), the rc system, shows extensive spectral evolution that can be described with four excited states (r₁*→r₂*→r₃*→r₄*→ground state). In the Perylene Orange calix[4]arene system (oc), a radical pair (ocRP) can be formed by photoinduced electron transfer (Hippius et al., J. Phys. Chem C 111:13988, 2007). In a simultaneous target analysis of the multichromophoric systems ocr, rcocr and ocrco the properties of rc and oc are integrated, and excitation energy transfer (EET) from o* to r* occurs. In addition, we demonstrate that the final Species Associated Difference Spectrum (SADS) also contains o bleach features that indicate an excitonic interaction, for ocr, rcocr and ocrco. In a simultaneous target analysis of rcg and gcrcg the properties of rc are integrated, and next to EET to g* we can resolve the formation of a new rcgRP that is formed from r₁* or r₂*, and represents a loss of 7 and 12%, respectively. In a simultaneous target analysis of ocrcg the properties of ocr and rcg are integrated, arriving at a consistent picture with an energy transfer quantum yield of formation of the excited state of the green PBI (g*) of 80%.