Merging Porphyrins with Organometallics: Synthesis and Applications

Abstract

The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or β position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal–carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.

Design of novel luminescent porphyrins bearing donor–acceptor groups

“…In the up-field region, two more signals are observed at 3.89 and -2.95 ppm, due to protons of the terminal NH 2 group and the inner protons NH of the porphyrin ring, respectively. 1 …”

“…MnO 2 was prepared according to the method previously reported in the literature [49]. 1 H NMR spectra of the intermediates and final compounds in CDCl 3 solution were recorded at room temperature on a Bruker Avance 400 MHz spectrometer, operating at 400 MHz and 100 MHz for 1 H and 13 C, respectively. The melting points of the obtained porphyrins could not be determined in a Fisher Instrument.…”

“…Yield 98%. 1 Absorption and fluorescence spectra of the porphyrinic molecules were recorded in CH 2 Cl 2 (spectrophotometric grade), which was purchased from Aldrich. Prior to use, this solvent was checked for spurious emission in the region of interest and was found to be satisfactory.…”

“…On the other hand, porphyrins have been employed in the synthesis of push-pull p-conjugated systems bearing donor-acceptor groups and in the design of dendritic molecules able to act as molecular antennae for photovoltaic applications [6][7][8]. The design of new porphyrin and multiporphyrinic arrays is very attractive due to its application in catalysis [1], nonlinear optics (NLO) [2], two photon absorption [3], and molecular wires [4]. Several electro-and photoactive units have been incorporated into porphyrins in order to tune their electronic and photophysical properties.…”

“…Porphyrins belong to a very important family of fluorophores that have been widely studied in macromolecular and materials science [1][2][3][4]. These chromophores are highly delocalized p-systems which are considered a unique category of ionic scavengers, whose recognition properties come from the heteroatoms present in their structure [5].…”