文摘
Perylene bisimide-calix[4]arene arrays composed of up to three different types of perylene bisimidechromophores (orange, red, and green PBIs) have been synthesized. Within these arrays, the individualchromophoric building blocks are positioned in defined spatial orientation and are easily replaceable by eachother without influencing the overall geometric arrangement of the supramolecular system. The specific opticalproperties of the individual chromophore facilitated the investigation of photoinduced processes very accuratelyby time-resolved emission and femtosecond transient absorption spectroscopy. A quantitative analysis of thephotophysical processes as well as their rate constants have been obtained by employing UV/vis absorption,steady state and time-resolved emission, femtosecond transient absorption spectroscopy, and spectrotemporalanalysis of the femtosecond transient absorption data. These studies reveal very efficient energy transferprocesses from the orange to the red PBI chromophoric unit (kET = 6.4 × 1011 s-1 for array or), from the redto the green PBI (kET = 4.0 × 1011s-1 for array rg), and slightly less efficient from the orange to the greenPBI (kET = 1.5 × 1011s-1 for array og) within these perylene bisimide-calix[4]arene arrays. The experimentallyobtained rate constants for the energy transfer processes are in very good agreement with those calculatedaccording to the Förster theory.