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

Aleksey E. Kuznetsov

[85] Šůcha L, Kotrlý S. Solution Equilibrium in Analytical Chemistry. London: Van Nostrand

[86] Chen G, Tao D. Effect of solution chemistry on flotability of magnesite and dolomite.

[87] Ringbom A. Complexation in Analytical Chemistry. New York: Interscience Publishers; 1963

[89] Sillén LG, Martell AE, Stability Constants of Metal-Ion Complexes, The Chemical Society,

[90] Beck MT. Chemistry of Complex Equilibria. New York: Van Nostrand Reinhold Co.; 1970 [91] Janecki D, Doktór K, Michałowski T. Determination of stability constants of complexes of

[92] Janecki D, Doktór K, Michałowski T. Erratum to "Determination of stability constants of

[93] Janecki D, Styszko-Grochowiak K, Michałowski T. The catenation and isomerisation effects on stability constants of complexes formed by some diprotic acids. Talanta.

[95] Zeidler E. Nonlinear Functional Analysis and its Applications: III: Variational Methods

[96] Sieniutycz S. Thermodynamic Approaches in Engineering Systems. Amsterdam: Elsevier; 2016 [97] Bertsekas DP. Nonlinear Programming. 2nd ed. Cambridge, MA: Athena Scientific; 1999

Talanta. 1999;49:943. http://www.sciencedirect.com/science/article/pii/S0039914099001745

HkL type in concentrated solutions of mixed salts. Talanta. 1999;48:1191-1197 http://

HkL type in concentrated solutions of mixed salts" [48 (1999) 1191].

[88] Rossotti H. The study of ionic equilibria. An introduction. London: Longman; 1978

International Journal of Mineral Processing. 2004;74(1–4):343-357

www.sciencedirect.com/science/article/pii/S0039914098003452

2000;52:555-562. http://www.ncbi.nlm.nih.gov/pubmed/18968016

and Optimization. New York: Springer Science +Business Media; 1985

Reinhold Comp.; 1975

MiKj

complexes of Mj

London, 1964; Supplement No. 1, 1971.

134 Descriptive Inorganic Chemistry Researches of Metal Compounds

Kj

[94] https://en.wikipedia.org/wiki/Gibbs\_free\_energy

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/67728

#### **Abstract**

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<sup>2</sup> or N2 ? (vi) Will the core‐modified porphyrins be able to form complexes with nanoparticles?

**Keywords:** metalloporphyrins, core modification, chalcogens, phosphorus, structural changes
