The flexibility of macrocyclic rings and the different spatial conformations of metallated and non-metallated macrocyclic compounds

Authors

DOI:

https://doi.org/10.33448/rsd-v12i10.43407

Keywords:

Macrocyclic complexes; Ring distortions; Macrocycle ligand; Tetrazamacrocycle.

Abstract

The chemistry of macrocyclic compounds is one of the areas with the greatest implications in several multi- and interdisciplinary areas, such as biological chemistry, materials chemistry, the chemistry of metal complexes and the so-called “supramolecular chemistry”. In fact, both in complexed and non-complexed form, such compounds are highly relevant. When it comes to so-called macrocyclic complexes, the well-known “macrocyclic effect” is the way in which the extraordinary kinetic and thermodynamic stabilities of such compounds are mentioned. Furthermore, macrocyclic coordination compounds are often formed, together with the concomitant formation of the macrocycle itself, that is, the precursors of macrocycle formation are united through the inducing-organizing action of the metal cation itself and/or coordination center. (which is known as “template effect”). There are several types of relevant macrocycles, such as, for example, tetraazamacrocycles, known for various importance, from the presence in prosthetic groups of relevant metalloproteins, such as porphyrins, among other macrocycles, to applications as photosensitizers in photodynamic therapy (PDT) and biosensors. The present study presents an introduction to the respective topic, covering an initial discussion on the different spatial conformations that free macrocycles or in their metallated forms can present and their implications. This work of literature revision aims to contribute to the discussion focused on such compounds, considering that their distinct spatial conformations are decisive for the respective structure-function relations, which has not always been considered in the different lines of research that pervade the chemistry of macrocycles.

References

Cheng, B., Munro, O. Q., Marques, H. M., & Scheidt, W. R. (1997). An Analysis of Porphyrin Molecular Flexibility – Use of Porphyrin Diacids. Journal of the American Chemical Society, 119, (44), 10732-42.

Ikezaki, A., Ikeue, T., & Nakamura, M. (2002b). Electronic Effects of Para-Substituents on the Configuration of Dicyano[Meso-Tetrakis(p-Substituted Phenyl)Porphyrinato]Iron(III) Complexes. Inorganica Chimica Acta, 335, 91-99.

Ikezaki, A., & Nakamura, M. (2002a) Effects of Solventes on the Electron Configurations of the Low-Spin Dicyano[meso-tetrakis(2,4,6,-triethylphenyl)porphyrinato]iron(III) Complex: Importance of the C-H…N Weak Hydrogen Bonding. Inorganic Chemistry, 41, (10), 2761-68.

Jentzen, W., Simpson, M. C., Hobbs, J. D., Song, X., Ema, T., Nelson, N. Y., Medforth, C. J., Smith, K. M., Veyrat, M., Mazzanti, M., Ramasseul, R., Marchon, J.C., Takeuchi, T., Goddard, W. A., & Shelnutt, J. A. (1995). Ruffling in Series of Nickel(II) meso-Tetrasubstituted Porphyrins as a Model for the Conserved Ruffling of the Heme of Cytochromes c. Journal of the American Chemical Society, 117, 11085-97.

Jianyu, L., & Yuanzong, L. (2004). Interaction of apoHb and various Fe-porphyrins. Journal of Molecular Catalysis A, 222, 75-80.

La Mar, G. N., Toi, H., & Krishnamoorthi, R. (1984). Proton NMR Investigation of the Rate and Mechanism of the Heme Rotation in Sperm Whale Myoglobin: Evidence for Intramolecular Reorientation about a Heme Twofold Axis. Journal of the American Chemical Society, 106, 6395-01.

Larsen, R. W., Nunez, D. J., Macleod, J., Shiemke, A. K., Musser, S. M., Nguyen, H. H., Ondrias, M. R., & Chan, S. I. (1992). Spectroscopic Characterization of Heme A Reconstituted Myoglobin. Journal of Inorganic Biochemistry, 48, 21-31.

Lindoy, L. F. (1989). Chemistry of Macrocyclic Ligand Complexes, Cambridge University Press: Cambridge.

Manso, C. M. C. P., Neri, C. R., Vidoto, E. A., Sacco, H. C., Ciuffi, K. J., & Iwamoto, L. S. (1999). Iamamoto, Y.; Nascimento, O. R.; Serra, O. A. Characterization of Iron(III)porphyrin-hidroxo Complexes in Organic Media through UV-vis and EPR Spectroscopies. Journal of Inorganic Biochemistry, 73, 85-92.

Moreira, L. M., Teixeira, A. O., & Lyon, J. P. (2022). Métodos Fototerapêuticos de relevância clínica. Research, Society and Development, 11, (5), e51411528589.

Munro, O. Q., Marques, H. M., Debrunner, P. G., Mohanrao, K., & Scheidt, W. R. (1995). Structural and Molecular Mechanics Studies on Highly Ruffled Low-Spin (Porphinato)iron(III) Complexes. Journal of the American Chemical Society, 117, 935-54.

Nakamura, M., Ikeue, T., Ikezaki, A., Ohgo, Y., & Fujii, H. (1999). Electron Configuration of Ferric Ions in Low-Spin (Dicyano)(meso-tetraarylporphyrinato)iron(III) Complexes. Inorganic Chemistry, 38, 3857-62.

Pereira, A. S., Shitsuka, D. M., Parreira, F. J., & Shitsuka, R. (2018). Metodologia da pesquisa científica. [free e-book/repositório.ufsm.br]. Santa Maria/RS. Ed. UAB/NTE/UFSM. https://www.ufsm.br/app/uploads/sites/358/2019/02/Metodologia-da-Pesquisa-Cientifica_final.pdf

Santucci, R., Ascoli, F., La Mar, G. N., Pandey, R. K., & Smith, K. M. (1993). Reconstitution of Horse Heart Myoglobin with Hemins Methylated at 6- or 7- positions: a Circular Dichroism Study. Biochimica et Biophysica Acta, 1164, 133-37.

Schweitzer-Stenner, R., & Bigman, D. (2001). Electronic and Vibronic Contributions to the Band Splitting in Optical Spectra of Heme Proteins. The Journal of Physical Chemistry B, 105, 7064-65.

Sima, J., & Makanova, J. (1997). Photochemistry of iron(III) complexes. Coordination Chemistry Reviews, 160, 161-89.

Stadler, E.; Estudos de Reatividade de Complexos Macrocíclicos de Ferro(II). São Paulo-SP, 143p. Tese (Doutorado) Instituto de Química, Universidade de São Paulo. Brasil. 1988.

Teraoka, J., Yamamoto, N., Matsumoto, Y., Kyogoku, Y., & Sugeta, H. (1996). What Is the Crucial Factor for Vibrational Circular Dichroism in Hemoprotein Ligans? Journal of the American Chemical Society, 118, 8875-78.

Toma, H. E., & Araki, K. (2000). Supramolecular Assemblies of Ruthenium Complexes and Porphyrins. Coordination Chemistry Reviews, 196, 307-29.

Walker, F. A. (1980). Models of the Cytochromes b. 1. Effect of Substituents, Axial Ligand Plane Orientation, and Possible Axial Ligand Bond Strain on the Pyrrole Proton Shifts of a Series of Low-Spin Monosubstituted Tetraphenylporphinatoiron(III)-Bisimidazole Complexes. Journal of the American Chemical Society, 102, (9), 3254-56.

Walker, F. A. (1999). Magnetic spectroscopic (EPR, ESEEM, Mössbauer, MCD and NMR) studies of low-spin ferriheme centers and their corresponding heme proteins. Coordination Chemistry Reviews, 185-186, 471-34.

Walker, F. A. (2004). Models of the Bis-Histidine-Ligated Electron-Transferring Cytochromes. Comparative Geometric and Electronic Structure of Low-Spin Ferro- and Ferrihemes. Chemical Reviews, 104, (2), 589-15.

Walker, F. A., & Benson, M. (1980). Entropy, Enthalpy, and Side Arm Porphyrins. 1. Thermodynamics of Axial Ligand Competition between 3-picoline and a Series of 3-Pyridil Ligands Covalently Attached to Zinc Tetraphenylporphyrin. Journal of the American Chemical Society, 102, 5530-38.

Wolowiec, S., Latos-Graznski, L., Mazzanti, M., & Marchon, J. (1997). Low-Spin Iron(III) Chiroporphyrins: 1H NMR Studies of Cyanide and Substituted Imidazole Coordination. Inorganic Chemistry, 36, 5761-71.

Wolowiec, S., Latos-Graznski, L., Toronto, D., & Marchon, J. (1998). Stabilization of the Less Common (dxz,dyz)4(dxy)1 Iron(III) Porpyrin Ground Electronic State: 1H NMR Investigations of Iron(III) 5,10,15,20-Tetracyclohexylporphyrin. Inorganic Chemistry, 37, (25), 724-32.

Yamamoto, Y., Nakashima, T., Kawano, E., & Chujô, R. (1998). 1H NMR Investigations of the Influence of the Heme Orientation on Functional Properties of Myoglobin. Biochimica et Biophysica Acta, 138, 349-62.

Zhang, H., Simonis, U., & Walker, F. A. (1990). Models of the Cytochrome b. 7. Novel Features in the Proton Nuclear Magnetic Resonance Spectra of Mono-Ortho-Substituted DiakylamidoTetraphenylporphinatoiron(III) Complexes. Journal of the American Chemical Society, 112, (16), 6124-26.

Zhu, Y., Ownby, D. W., Riggs, C. K., Nolasco, N. J., Stoops, J. K., & Riggs, A. F. (1996). Assembly of the Gigantic Hemoglobin of the Earthworm Lumbricus terrestris. Journal of Biological Chemistry, 271, (47), 30007-21.

Published

03/10/2023

How to Cite

MOREIRA, L. M.; TEIXEIRA, A. de O. .; LYON, J. P. . The flexibility of macrocyclic rings and the different spatial conformations of metallated and non-metallated macrocyclic compounds. Research, Society and Development, [S. l.], v. 12, n. 10, p. e28121043407, 2023. DOI: 10.33448/rsd-v12i10.43407. Disponível em: https://rsdjournal.org/index.php/rsd/article/view/43407. Acesso em: 23 dec. 2024.

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Section

Review Article