Two giant calix[n]phyrin derivatives namely calix- (4) and calixphyrin (5), involving two and four BF2 units, respectively, were prepared through the condensation of the bis-naphthobipyrrolylmethene-BF2 complex (3) with pentafluorobenzaldehyde. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82×105 m−1 cm−1, respectively) in the near-IR region, which was taken as initial evidence for strong excitonic coupling within these cyclic multi-chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from fluorescence, time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements. Support for these experimental findings came from theoretical studies. Theory and experiment confirmed that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.
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