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A pair of giant calix[n]phyrin derivatives namely calix[8]- ( 4 ) and calix[16]phyrin ( 5 ), involving two and four BF 2 units, respectively, were prepared via the condensation of the bisnaphthobipyrrolylmethene-BF 2 complex ( 3 ) with pentafluorobenzaldehyde. Both systems and precursor 3 were fully characterized, including via single crystal X-ray diffraction analyses. 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. This observation was taken a