Covalent nano-clip and nano-box compounds based on free base porphyrins

Novel nano-clip and nano-box compounds were obtained by reaction between dibromomethane and 5,15-di[p-(9-methoxytriethylenenoxy)phenyl-10,20-di[p-hydroxyphenyl]porphyrin. The molecular architecture varies from a co-facial (nano-clip) to a four wall-box (nano-box) structure. The products were characterized by H-1 NMR and UV-vis spectroscopy and MALDI-TOF mass spectrometric analysis. The UV vis spectra of the nano-clip showed a modification of the characteristic porphyrin soret and Q bands, with respect to the monomer and cyclic tetramer, as a probable consequence of a hybrid orbital deformation (HOD) phenomenon involving the two porphyrin it rings forced to a closer co-facial spatial arrangement. The spatial distance between the two co-facial porphyrin units, and therefore the molecular cavity size, can be modified inducing an electrostatic repulsion by means of a reversible protonation of the pyrrolic cores. The H-1 NMR spectra of the nano-box showed a strong high-field shift of some aromatic and ether protons present in the upper and lower rim of the molecular box. (C) 2011 Elsevier Ltd. All rights reserved.