Design of Novel Classes of Building Blocks for Nanotechnology: Core‐Modified Metalloporphyrins and Their Derivatives

Metalloporphyrins and related macrocycles have been of great interest due to their role in biology and their numerous technological applications. Engineering of the porphy‐ rins by replacing pyrrole nitrogens with other elements is a highly promising approach for tuning properties of porphyrins. To date, numerous efforts have been made to the modification of the porphyrin core with main‐group elements, such as chalcogens (O, S, Se) and phosphorus. Thus, the modification of the porphyrin core by incorpora‐ tion of heteroatoms instead of nitrogens is a very promising strategy for obtaining novel compounds with unusual optical, electrochemical and coordinating properties as well as reactivity. These novel compounds can be used as building blocks in various nanotech‐ nological applications. Within the framework of this research, the following questions can be formulated: (i) what structures will core‐modified porphyrins adopt? (ii) How will electronic properties of core‐modified porphyrins differ from those of common tetrapyr‐ roles? (iii) Will the core‐modified porphyrins be able to form stacks and other arrays like regular porphyrins? (iv) Can core‐modified porphyrins form complexes with fullerenes? (v) Can core‐modified porphyrins activate small molecules, e.g. O 2 or N 2 ? (vi) Will the core‐modified porphyrins be able to form complexes with nanoparticles?