Synthesis of Multi(metallo)porphyrin Dendrimers through Nucleophilic Aromatic Substitution on meso-Pyrimidinyl Substituted Porphyrins

Abstract

A convergent synthetic strategy toward novel all-porphyrin dendrimers, which can be regarded as synthetic model systems of the natural photosynthetic light-harvesting antennae, was successfully explored. The dendron propagation, based on nucleophilic aromatic substitution reactions on a meso-dichloropyrimidinyl substituted porphyrin AB2 monomer, was carried out up to the second-generation dendron, and the used approach was proven to be compatible with the stepwise introduction of different metals in the successive generations. Three different metals (Pt, Zn, and Ni) could be introduced in the second-generation heptaporphyrin dendron. By applying analogous meso-dichloropyrimidinyl substituted porphyrin cores, novel multiporphyrin dendrimers were obtained.

Synthesis and photochemical properties of 3,6-di-tert-butyl-9H-carbazole derivatives

“…[2][3][4][5][6]. Thus, carbazole derivatives are used as synthons for preparation of luminophores [7], and branched 3,6disubstituted derivatives of carbazole are applied as building blocks for creation of more complex organic molecules [8]. Compounds of this type are now used for the synthesis of OLEDs because of their high hole conductivity, photochemical stability, and electroconductivity [9][10][11].…”

Spectral-Luminescent Properties of meso-Tetraarylporphyrins Revisited: The Role of Aryl Type, Substitution Pattern and Macrocycle Core Protonation

“…The fluorescence spectra and fluorescence quantum yields of all mono-and diprotonated species are reported and the relationship with the molecular structure of the compounds was analyzed in detail. The reported results are of particular importance for the interpretation (prediction) of the optical features of dendritic structures with a porphyrin core, [58][59][60][61] especially with respect to the acid-base equlibria in the porphyrin macrocycle core.…”

Synthetic Aspects of Porphyrin Dendrimers

“…Our group has also contributed to the field of all‐porphyrin dendrimers. In 2006 we reported an efficient synthetic protocol for novel multiporphyrin dendrons and dendrimers, constructed through consecutive S N Ar reactions with meso ‐(dichloropyrimidinyl)porphyrinic building blocks 76. The dendron propagation involved a (high‐yielding) S N Ar reaction with the peripheral AB 3 porphyrin 51a , decorated with di‐ tert ‐butylphenyl groups to afford high solubility and thereby enabling easy synthetic routine handling and characterization, and the meso ‐(dichloropyrimidinyl)‐substituted porphyrin AB 2 monomer 71a , with subsequent deprotection of the benzyl‐protected phenolic focal moiety (Scheme ).…”