Synthetic strategies and porphyrin building blocks for unsymmetrical multichromophores

Transition Metal Catalysis in Porphyrin Modifications

“…[33] Heck and Sonogashira reactions are also widely employed for the synthesis of bisporphyrin compounds with different linkers including acetylenic fragments, [34] the latter approach was helpful in the synthesis of porphyrin trimers as well. [35] Catalytic amination and alkoxylation reactions were successfully applied to the synthesis of porphyrin dimers and trimers. [36] Cu(I)-catalyzed 1,3-dipolar cycloaddition reactions can be also used for the synthesis of porphyrin dyads with 1,2,3-triazole linkers.…”

Quantum-Сhemical Insight into the Reactivity of 5-Bromo-10,20-diaryl-porphyrins towards Nucleophiles

“…[20][21][22][23] Moreover, meso-functionalization of diarylporphyrins is possible also by the nucleophilic addition of alkyl-or aryllithium reagents to the porphyrins followed by the oxidation of the resulting porphyrinogens. [6,24,25] In the present work we evaluated the reactivity of 5-bromoporphyrins towards the nucleophilic substitution reaction (Scheme 1) using the widely available level of DFT calculations. Analyzing the limited experimental data, it is possible to speculate that the electronic effects of a substituent at 15 position significantly influence the process.…”

Stirring the porphyrin alphabet soup—functionalization reactions for porphyrins

“…Although this reaction is not very selective and results in mixtures, it can be controlled to some extent 235 by the number of equivalents of NBS used. 34 The bromoporphyrins can then be used for analogous sequences to yield the A x or ABCD porphyrins. Obviously, any other meso functionalization reaction (e.g., formylation, nitration, etc.)…”

“…We were especially interested in facilitating methods that would allow further modification of these systems through follow-up chemistry and a more detailed 730 modulation of the electronic and structural properties through mixing of the substituent types on the individual porphyrin subunits. 34 The chemistry applied was similar to the one shown in Schemes 3 and 9 but obviously focused more on the use of synthons suitable 735 for further transformations. 34 Scheme 17 gives a few selected examples of the building blocks developed and synthetic sequences for the preparation of di-and trimeric porphyrin systems with unsymmetrical substituent patterns and linker groups.…”

“…34 The chemistry applied was similar to the one shown in Schemes 3 and 9 but obviously focused more on the use of synthons suitable 735 for further transformations. 34 Scheme 17 gives a few selected examples of the building blocks developed and synthetic sequences for the preparation of di-and trimeric porphyrin systems with unsymmetrical substituent patterns and linker groups. Due to their utility in nonlinear optical porphyrins, 5d,76 we initially concentrated 740 on alkynyl-linked systems.…”