Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives

Gruden, Maja; Grubišić, Sonja; Coutsolelos, Athanassios G.; Niketić, Svetozar R.

doi:10.1016/s0022-2860(01)00550-6

Cited by 22 publications

(26 citation statements)

References 37 publications

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“…As in our previous MM study [15], the initial structures for tetrabromo TPP were chosen on the basis of the most symmetrical substitution pattern of the halogens and comprised: 2,8,12,18-tetrabromo-TPP (transtrans, or tt) isomer; 2,3,12,13-tetrabromo-TPP (cis-trans, or ct) isomer; and 2,7,12,17-tetrabromo-TPP (windmill, or wm) isomer. So far, the cis-trans (ct) pattern ( Fig.…”

Section: Introductionmentioning

confidence: 56%

“…Computational details and force field parameters are particularized in [15]. The only new parameters are for bromine atom and the values are given in Table 1.…”

Section: Computational Proceduresmentioning

confidence: 99%

“…For each of the equilibrium structures obtained by the energy minimization procedure we have carried the normal-coordinate structural decomposition (NSD) [27] of the out-of-plane deformation into the six basic symmetry types (dom, sad, wav ðxÞ ; wav ðyÞ , ruf and pro) using a simplified procedure described in our previous [15] paper.…”

Section: Computational Proceduresmentioning

confidence: 99%

“…The conformers obtained by MM calculations are stereochemically characterized, compared with available X-ray crystal structures [25,26], analyzed by the normal-coordinate structural decomposition (NSD) method [27], and also compared with the conformers obtained in our previous MM study on chloro instead of bromo halogenated substituents [15]. Our results may be of interest for the studies of fine-tuning of porphyrin properties affected by non-planarity [28] as well as for general elucidation of the interplay between steric and electronic factors influencing the non-planarity of porphyrin structures.…”

Section: Introductionmentioning

confidence: 99%

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Conformational analysis of octa- and tetrabromo tetraphenylporphyrins and their Ni(II) and Tb(III) complexes

Gruden

Grubišić

Niketić

2004

Journal of Inorganic Biochemistry

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Section: Introductionmentioning

confidence: 56%

“…Computational details and force field parameters are particularized in [15]. The only new parameters are for bromine atom and the values are given in Table 1.…”

Section: Computational Proceduresmentioning

confidence: 99%

Section: Computational Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Conformational analysis of octa- and tetrabromo tetraphenylporphyrins and their Ni(II) and Tb(III) complexes

Gruden

Grubišić

Niketić

2004

Journal of Inorganic Biochemistry

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“…The presence of ␤-pyrrolic substituents, as well as the presence of metal centers in meso-tetraphenylporphyrins [14,15] can alter the planarity of the porphyrin macrocycle. In the last two decades, the relation between the nonplanarity of several porphyrins and their function in natural systems have been investigated [16,17].…”

mentioning

confidence: 99%

Characterization of isomeric cationic porphyrins with β-pyrrolic substituents by electrospray mass spectrometry: The singular behavior of a potential virus photoinactivator

Izquierdo

Barros

Santana-Marques

et al. 2007

J. Am. Soc. Mass Spectrom.

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Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/ MS) have been used to differentiate the 2-and 4-methylpyridyl isomers of free-base and metallated cationic ␤-vinylpyridylporphyrins. The analysis by ESI-MS/MS of the deuterated analogs and semiempirical calculations of structural and electronic parameters were also undertaken. The two free-base isomers are easily differentiated by ESI-MS/MS but the presence of a metallic center renders differentiation of the metallated isomers less effective. The data acquired show that of all the studied compounds, the free-base 2-methylpyridyl isomer, which was operative in the in vitro photoinactivation of Herpes simples virus, has a different gas-phase behavior. Local distortion of the macrocycle due to the presence of the ␤-vinylpyridyl substituent occurs for all the compounds, but a different electron density distribution can account for the observed gas-phase behavior of this potential virus photoinactivator. (J Am Soc Mass Spectrom 2007, 18, 218 -225 Viruses are responsible for a large number of infectious diseases. In particular, the Herpes simplex virus is one of the most common agents responsible for viral infections in man [5]. From preliminary virus inactivation studies carried out with Herpes simplex virus type 1 (HSV-1) using the cationic porphyrins 1 and 2 (Scheme 1), we have observed that despite their structural resemblance and their similar photocytotoxicity profiles, Compound 1 was very effective in the photoinactivation of the virus, whereas Compound 2 displayed no virucidal effect in the same conditions [6].Electrospray ionization mass spectrometry (ESI-MS) was successfully applied to characterize porphyrins as early as 1991 [7] and both ESI-MS [8 -11] and tandem mass spectrometry (ESI-MS/MS) [12,13] have been used to study neutral and cationic porphyrins since then. We wanted to know if the two porphyrin isomers, 1 and 2, could be differentiated by ESI-MS/MS and if the informa-

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Tuning the Electrochemistry of Free‐Base Porphyrins in Acidic Nonaqueous Media: Influence of Solvent, Supporting Electrolyte, and Ring Substituents

et al. 2015

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International audienceA detailed study of reduction potentials, electroreduction mechanisms, and acid-base chemistry was carried out on two series of free-base porphyrins in nonaqueous media. The first series is represented by four -pyrrole-substituted tetraphenylporphyrin (TPP) derivatives, two of which are planar and two of which are nonplanar in their nonprotonated form. The second comprises porphyrins with 0-4 meso-phenyl groups on the macrocycle. Equilibrium constants for the conversion of each neutral porphyrin to its diprotic [H4P](2+) form were determined and the electrochemistry was then elucidated as a function of: 1)type of nonaqueous solvent, 2)anion of supporting electrolyte, 3)porphyrin ring substituents, and 4)concentration of acid added to solution. Spectroelectrochemistry was used to characterize absorption spectra of each electroreduced species and, when combined with results of the above studies, significantly improves our ability to tune redox reactivity of these types of compounds

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Conformational analysis of octa- and tetrahalogenated tetraphenylporphyrins and their metal derivatives

Cited by 22 publications

References 37 publications

Conformational analysis of octa- and tetrabromo tetraphenylporphyrins and their Ni(II) and Tb(III) complexes

Conformational analysis of octa- and tetrabromo tetraphenylporphyrins and their Ni(II) and Tb(III) complexes

Characterization of isomeric cationic porphyrins with β-pyrrolic substituents by electrospray mass spectrometry: The singular behavior of a potential virus photoinactivator

Tuning the Electrochemistry of Free‐Base Porphyrins in Acidic Nonaqueous Media: Influence of Solvent, Supporting Electrolyte, and Ring Substituents

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