Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives
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2001
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A new maximally diagonal force field for molecular modelling of metalloporphyrins is developed and optimized on the crystal structures of nickel(II) porphine, nickel(II) mono-tert-butylporphyrin and nickel(II) di-tert-butylporphyrin. It is then used to investigate non-planar distortions of octa- and tetrachloro tetraphenylporphyrins (TPP) and their Ni(II) and Tb(III) complexes. Molecular mechanics (MM) calculations reproduced very well the structure of Tb(III) octachloro-TPP (so far the only example of a crystallographically characterized chloro TPP metal derivative). Normal-coordinate structural decomposition (NSD) analysis was performed on the equilibrium structures obtained by MM calculations. As expected, sad distortion dominates in octachloro structures irrespective of the presence or the size of the central metal atom; dom distortion dominates in tetrachloro structures with large Th(III) central atom, while sad, ruf, wav and pro distortions are present in various amounts in other... tetrachloro structures (TPP free base and Ni(II) complex) depending on the pattern of peripheral chloro substitution on the pyrrole rings. Other observed regularities are: reduction of the conformational flexibility of the porphyrin core upon metallation, and increase of the dihedral angle between the phenyl groups and the mean LSQ plane of the porphyrin core, as well as the overall increase in structural regularity upon the increase of the size of the central metal atom. (C) 2001 Elsevier Science B.V. All rights reserved.
Ključne reči:
molecular mechanics / porphyrins / porphyrin conformations / normal-coordinate structural decomposition / Ni(II) porphyrin complexes / Tb(III) porphyrin complexesIzvor:
Journal of Molecular Structure, 2001, 595, 1-3, 209-224Izdavač:
- Elsevier Science Bv, Amsterdam
DOI: 10.1016/S0022-2860(01)00550-6
ISSN: 0022-2860
WoS: 000171376400023
Scopus: 2-s2.0-0000405610
Kolekcije
Institucija/grupa
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Gruden-Pavlović, Maja AU - Grubišić, Sonja AU - Coutsolelos, AG AU - Niketic, SR PY - 2001 UR - https://cherry.chem.bg.ac.rs/handle/123456789/472 AB - A new maximally diagonal force field for molecular modelling of metalloporphyrins is developed and optimized on the crystal structures of nickel(II) porphine, nickel(II) mono-tert-butylporphyrin and nickel(II) di-tert-butylporphyrin. It is then used to investigate non-planar distortions of octa- and tetrachloro tetraphenylporphyrins (TPP) and their Ni(II) and Tb(III) complexes. Molecular mechanics (MM) calculations reproduced very well the structure of Tb(III) octachloro-TPP (so far the only example of a crystallographically characterized chloro TPP metal derivative). Normal-coordinate structural decomposition (NSD) analysis was performed on the equilibrium structures obtained by MM calculations. As expected, sad distortion dominates in octachloro structures irrespective of the presence or the size of the central metal atom; dom distortion dominates in tetrachloro structures with large Th(III) central atom, while sad, ruf, wav and pro distortions are present in various amounts in other tetrachloro structures (TPP free base and Ni(II) complex) depending on the pattern of peripheral chloro substitution on the pyrrole rings. Other observed regularities are: reduction of the conformational flexibility of the porphyrin core upon metallation, and increase of the dihedral angle between the phenyl groups and the mean LSQ plane of the porphyrin core, as well as the overall increase in structural regularity upon the increase of the size of the central metal atom. (C) 2001 Elsevier Science B.V. All rights reserved. PB - Elsevier Science Bv, Amsterdam T2 - Journal of Molecular Structure T1 - Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives VL - 595 IS - 1-3 SP - 209 EP - 224 DO - 10.1016/S0022-2860(01)00550-6 ER -
@article{ author = "Gruden-Pavlović, Maja and Grubišić, Sonja and Coutsolelos, AG and Niketic, SR", year = "2001", abstract = "A new maximally diagonal force field for molecular modelling of metalloporphyrins is developed and optimized on the crystal structures of nickel(II) porphine, nickel(II) mono-tert-butylporphyrin and nickel(II) di-tert-butylporphyrin. It is then used to investigate non-planar distortions of octa- and tetrachloro tetraphenylporphyrins (TPP) and their Ni(II) and Tb(III) complexes. Molecular mechanics (MM) calculations reproduced very well the structure of Tb(III) octachloro-TPP (so far the only example of a crystallographically characterized chloro TPP metal derivative). Normal-coordinate structural decomposition (NSD) analysis was performed on the equilibrium structures obtained by MM calculations. As expected, sad distortion dominates in octachloro structures irrespective of the presence or the size of the central metal atom; dom distortion dominates in tetrachloro structures with large Th(III) central atom, while sad, ruf, wav and pro distortions are present in various amounts in other tetrachloro structures (TPP free base and Ni(II) complex) depending on the pattern of peripheral chloro substitution on the pyrrole rings. Other observed regularities are: reduction of the conformational flexibility of the porphyrin core upon metallation, and increase of the dihedral angle between the phenyl groups and the mean LSQ plane of the porphyrin core, as well as the overall increase in structural regularity upon the increase of the size of the central metal atom. (C) 2001 Elsevier Science B.V. All rights reserved.", publisher = "Elsevier Science Bv, Amsterdam", journal = "Journal of Molecular Structure", title = "Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives", volume = "595", number = "1-3", pages = "209-224", doi = "10.1016/S0022-2860(01)00550-6" }
Gruden-Pavlović, M., Grubišić, S., Coutsolelos, A.,& Niketic, S.. (2001). Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives. in Journal of Molecular Structure Elsevier Science Bv, Amsterdam., 595(1-3), 209-224. https://doi.org/10.1016/S0022-2860(01)00550-6
Gruden-Pavlović M, Grubišić S, Coutsolelos A, Niketic S. Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives. in Journal of Molecular Structure. 2001;595(1-3):209-224. doi:10.1016/S0022-2860(01)00550-6 .
Gruden-Pavlović, Maja, Grubišić, Sonja, Coutsolelos, AG, Niketic, SR, "Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives" in Journal of Molecular Structure, 595, no. 1-3 (2001):209-224, https://doi.org/10.1016/S0022-2860(01)00550-6 . .