Core protonation of meso-tetraphenylporphyrin with tetrafluoroboric acid: unusual water-mediated hydrogen bonding of H4tpp2+ to the counterion

Rayati, Saeed; Zakavi, Saeed; Ghaemi, Akbar; Carroll, Patrick J.

doi:10.1016/j.tetlet.2007.11.140

Cited by 22 publications

(13 citation statements)

References 15 publications

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“…According to data of Tables 1, 2, 3, and 4 and Table S1-S3, the larger shi of the Soret band for a given H 2 t(py)P occurs in the protonation with HCl. e size and hydrogen bond acceptor ability of the counteranion of porphyrin dications play an important role in the extent of saddling of porphyrin core and stability of the adduct [1,6,8,9,20]. It has been shown that in a series of diprotonated mesotetra(phenyl)porphyrin, [H 4 TPP](X) 2 (X = F, Cl, Br, I), the degree of saddling of porphyrin core increases with increasing size of the halide.…”

Section: Shi Of the Soret And Q(00) Bands Of H 2 T(py)p Inmentioning

confidence: 99%

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Effects of Core and/or Peripheral Protonation ofmeso-Tetra(2-, 3-, and 4-pyridyl)Porphyrin andmeso-Tetra(3-methylpyridyl)Porphyrin on Their UV-vis Spectra

Zakavi

Rahiminezhad

Mojarrad

et al. 2013

Journal of Spectroscopy

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Core and/or peripheral protonation ofmeso-tetra(pyridyl)porphyrins, H2(py)P, with weak and strong acids have been studied by UV-vis spectroscopy. The results support the proposal that the position of the Soret as well as the Q(0,0) bands of the dications is influenced byπdonation from themesosubstituents to the porphyrin core. The red shift of the Q(0,0) band of H2t(py)P dications with 2-, 3-, and 4-pyridyl substituents does not correlate with the order ofπelectron donor ability of themesogroups. The decreased electron donation from the central nitrogen atoms to the acids on going from 3-pyridyl group to 4- and 2-pyridyl ones has been used to explain this observation. In spite of the negative effect of N-methylation of pyridyl substituents on the basicity of the central nitrogen atoms ofmeso-tetra(3-methylpyridyl)porphyrin, H2t(3-Mepy)P, protonation of H2t(3-Mepy)P occurs with weak and strong acids. The blue shift of the Q(0,0) bands upon protonation of H2t(3-Mepy)P with weak and strong acids clearly shows the importance of resonance interactions between theπ-systems of porphyrin and the aryl substituents on the position of the band.

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Section: Shi Of the Soret And Q(00) Bands Of H 2 T(py)p Inmentioning

confidence: 99%

“…Core protonation of porphyrins with weak and strong Lewis and protic acids has been the subject of many studies since the late 1970s [1][2][3][4][5][6][7][8][9][10]. X-ray crystallographic studies on many porphyrin dications have shown a distorted (mainly saddled) conformation of the aromatic macrocycle [1,[4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Effects of Core and/or Peripheral Protonation ofmeso-Tetra(2-, 3-, and 4-pyridyl)Porphyrin andmeso-Tetra(3-methylpyridyl)Porphyrin on Their UV-vis Spectra

Zakavi

Rahiminezhad

Mojarrad

et al. 2013

Journal of Spectroscopy

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“…Other structures with 22,24-dihydro-5,10,15,20-tetraphenylporphyrindiium dications contain a number of combinations of anions and solvents: porphyrin bis(hydrogen sulfate) methanol disolvate (Senge & Kalisch, 1999), porphyrin diperchlorate benzene monosolvate (Cheng et al, 1997), porphyrin bis(tetrafluoroborate) chloroform monosolvate dihydrate (Rayati et al, 2008) and porphyrin diperchlorate methanol monosolvate (Senge et al, 1994;Senge & Kalisch, 1999).…”

Section: Figurementioning

confidence: 99%

Influence of chloroform on crystalline products yielded in reactions of 5,10,15,20-tetraphenylporphyrin with HCl and copper(II) salts

Plaza¹,

Chojnacki²

2011

Acta Crystallogr C

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Chloroform was found to occupy the lattice of the protonated porphyrin and to promote crystallization of a different polymorphic form of a metalloporphyrin. The structure of 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride chloroform octasolvate, C(44)H(32)N(4)(2+)·2Cl(-)·8CHCl(3), (I), in the solid state is described and compared with related solvates. The porphyrin macrocycle displays a distorted saddle shape, with chloride anions above and below the ring. Seven chloroform molecules are bound via C-H···Cl hydrogen bonds, while the link with the eighth solvent molecule is weaker. A new monoclinic polymorph of (5,10,15,20-tetraphenylporphyrinato)copper(II), [Cu(C(44)H(28)N(4))], (II), crystallized from chloroform, is also presented.

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“…In H 4 TPP ] 2 two water molecules bridge the dications and corresponding counter anions above and below the porphyrin mean plane. [37] In the a 4 -P1 structures,awater molecule interacting with inner core system is observedo nly on the side with apredominantn umber of ammonium groups forming an ew "Tshaped" hydrogen-bonding complex feature (Figure 10 a) 4 structures, af ace selectivity in the porphyrinanion interactions is observed without the core bridging water molecule. Thisi nteraction forms aY -shaped hydrogen bonded complex in which anionsformasemi-symmetrical H-bond (Figure 10 b).…”

Section: Single-crystal X-ray Crystallographic Analysismentioning

confidence: 99%

Elucidating Atropisomerism in Nonplanar Porphyrins with Tunable Supramolecular Complexes

Norvaiša

O’Brien

Gibbons

et al. 2020

Chemistry A European J

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Atropisomerism is afundamental feature of substituted biaryls resulting from rotation aroundt he biaryl axis. Different stereoisomers are formed due to restricted rotation about the single bond, asituation often found in substituted porphyrins.P reviously NMR determination of porphyrin atropisomers proved difficult, if not almosti mpossible to accomplish, due to low resolution or unresolvable resonance signals that predominantly overlapped.H ere, we shed some light on this fundamentali ssue found in porphyrinoid stereochemistry.U sing benzenesulfonic acid (BSA) for host-guest interactions andp erforming 1D, 2D NMR spectro-scopic analyses, we werea ble to characterize all four rotamers of the nonplanar 5,10,15,20-tetrakis(2-aminophenyl)-2,3,7,8,12,13,17,18-octaethylporphyirin as restricted H-bonding complexes.A dditionally,X-ray structural analysisw as used to investigate aspects of the weakh ost-guest interactions. Ad etailed assignment of the chemical signals suggests charge-assisted complexation as ak ey to unravel the atropisomeric enigma. From am ethod development perspective, symmetry operations unique to porphyrin atropisomers offer an essential handle to accurately identify the rotamers using NMR techniques only.

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Core protonation of meso-tetraphenylporphyrin with tetrafluoroboric acid: unusual water-mediated hydrogen bonding of H4tpp2+ to the counterion

Cited by 22 publications

References 15 publications

Effects of Core and/or Peripheral Protonation ofmeso-Tetra(2-, 3-, and 4-pyridyl)Porphyrin andmeso-Tetra(3-methylpyridyl)Porphyrin on Their UV-vis Spectra

Effects of Core and/or Peripheral Protonation ofmeso-Tetra(2-, 3-, and 4-pyridyl)Porphyrin andmeso-Tetra(3-methylpyridyl)Porphyrin on Their UV-vis Spectra

Influence of chloroform on crystalline products yielded in reactions of 5,10,15,20-tetraphenylporphyrin with HCl and copper(II) salts

Elucidating Atropisomerism in Nonplanar Porphyrins with Tunable Supramolecular Complexes

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