C − H···π interactions in the metal-porphyrin complexes with chelate ring as the h acceptor

Specific C − H···π interactions with the π-system of porphyrinato chelate ring were found in crystal structures of transition metal complexes from the CSD and statistical analysis of geometrical parameters for intramolecular and intermolecular interactions was done. DFT calculations on a model system show that energy of the interaction is 1.58 kcal/mol and that the strongest interaction occurs when the distance between hydrogen atom and the center of the chelate ring is 2.6 Å. This prediction is in good agreement with the distances for intermolecular interactions found in the crystal structures. In many cases the intramolecular interaction distances are much shorter than 2.6 Å, and these short distances appear to be caused by geometrical constrains. The C − H···π interactions with chelate ring of porphyrinato ligand can be important in biomolecules with porphyrin as they can influence the structure, contribute to the stability and play some role in function of biomolecules.Physical chemistry 2004 : 7th international conference on fundamental and applied aspects of physical chemistry; Belgrade (Serbia); 21-23 September 200

Uloga kompleksa metala u evoluciji života

The role of metal complexes in the evolution of life is very important. Using the magnesium complex of porphyrin, chlorophyll, living organisms started to synthesise organic molecules converting solar energy to chemical energy. Iron complexes of porphyrin in cytochromes made possible to use oxygen for combustion of organic molecules and liberate energy necessary for living organisms. Transport of oxygen to cells in multicelled creatures and evolution of large organisms was also possible due to iron complexes of porphyrin, but in molecule of hemoglobin

Eksperimentalni i teorijski dokazi da je Cu(II) jon u vodenom rastvoru pentakoordinovan

The structure of the hydrated Cu(II) complex was determined by both neutron diffraction and first-principles molecular dynamics. In contrast with the generally accepted picture, which assumes an octahedrally solvated Cu(II) ion, new experimental and theoretical results favor fivefold coordination. The simulation reveals that the solvated complex undergoes frequent transformations between square pyramidal and trigonal bipyramidal configurations. The preference of the Cu(II) ion for fivefold instead of six fold coordination, which occurs for other cations of comparable charge and size, results from Jahn-Teller destabilization of the octahedral complex

Eksperimentalni i teorijski dokazi da je Cu(II) jon u vodenom rastvoru pentakoordinovan

The structure of the hydrated Cu(II) complex was determined by both neutron diffraction and first-principles molecular dynamics. In contrast with the generally accepted picture, which assumes an octahedrally solvated Cu(II) ion, new experimental and theoretical results favor fivefold coordination. The simulation reveals that the solvated complex undergoes frequent transformations between square pyramidal and trigonal bipyramidal configurations. The preference of the Cu(II) ion for fivefold instead of six fold coordination, which occurs for other cations of comparable charge and size, results from Jahn-Teller destabilization of the octahedral complex

Intramolecular C-H⋯π interactions in metal-porphyrin complexes

Cambridge Structural Database (CSD) was screened in order to find intramolecular C-H⋯π interactions with a chelate ring of coordinated porphyrin. It was found 154 crystal structures with 244 intramolecular C-H⋯π interactions in transition metal complexes with derivatives of porphyrin. Comparison of interacting distances indicates that interactions of hydrogen atoms in positions 2 and 6 of axially coordinated pyridine are more favorable with ruffled than with planar porphyrin

Supplementary data for the article: Veljković, D. Ž.; Medaković, V. B.; Andrić, J. M.; Zarić, S. D. C-H/O Interactions of Nucleic Bases with a Water Molecule: A Crystallographic and Quantum Chemical Study. CrystEngComm 2014, 16 (43), 10089–10096. https://doi.org/10.1039/c4ce00595c

Supplementary material for: [https://doi.org/10.1039/c4ce00595c]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1868

Supplementary material for the article: Milovanović, M. M.; Andrić, J. M.; Medaković, V. B.; Djukic, J.-P.; Zarić, S. D. Investigation of Interactions in Lewis Pairs between Phosphines and Boranes by Analyzing Crystal Structures from the Cambridge Structural Database. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials 2018, 74 (3), 255–263. https://doi.org/10.1107/S2052520618003736

Supplementary material for: [https://doi.org/10.1107/S2052520618003736]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2157

Supplementary data for the article: Ninković, D. B.; Vojislavljević-Vasilev, D. Z.; Medaković, V. B.; Hall, M. B.; Brothers, E. N.; Zarić, S. D. Aliphatic-Aromatic Stacking Interactions in Cyclohexane-Benzene Are Stronger than Aromatic-Aromatic Interaction in the Benzene Dimer. Physical Chemistry Chemical Physics 2016, 18 (37), 25791–25795. https://doi.org/10.1039/c6cp03734h

Supplementary material for: [https://doi.org/10.1039/c6cp03734h]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2328]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/3324

Supplementary data for the article: Veljković, D. Ž.; Medaković, V. B.; Andrić, J. M.; Zarić, S. D. C-H/O Interactions of Nucleic Bases with a Water Molecule: A Crystallographic and Quantum Chemical Study. CrystEngComm 2014, 16 (43), 10089–10096. https://doi.org/10.1039/c4ce00595c

Supplementary material for: [https://doi.org/10.1039/c4ce00595c]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1868

Intramolecular C-H⋯π interactions in metal-porphyrin complexes

Cambridge Structural Database (CSD) was screened in order to find intramolecular C-H⋯π interactions with a chelate ring of coordinated porphyrin. It was found 154 crystal structures with 244 intramolecular C-H⋯π interactions in transition metal complexes with derivatives of porphyrin. Comparison of interacting distances indicates that interactions of hydrogen atoms in positions 2 and 6 of axially coordinated pyridine are more favorable with ruffled than with planar porphyrin