PbII ethynyl- and butadiynyl-bridged bis(phthalocyaninates) 1a–d, peripherally functionalized with n-butoxy moieties, have been synthesized by using Pd-catalyzed cross-coupling methodologies. Preliminary open-aperture Z-scan experiments with nanosecond pulses at 550 nm on solutions of PbII bis(phthalocyaninates) 1b and 1d show strong reduction of the transmission at high intensities, although an irreversible optical behaviour is observed at the experimental time scale. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)