Tetraazuliporphyrin Tetracation

Sprutta, Natasza; Maćkowiak, Stanisław; Kocik, Marzena; Szterenberg, Ludmiła; Lis, Tadeusz; Latos‐Grażyński, Lechosław

doi:10.1002/ange.200900496

Cited by 13 publications

(9 citation statements)

References 45 publications

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“…For 21,23-divacataporphyrin, variable-temperature 1 been highlighted. [16,17] Recently, a relevant molecular pattern has been identified in tetraazuliporphyrin tetracation. [17] An analogous relationship that intertwines the hypothetical [18]annulenes of C 2h or lower symmetry, the porphyrin structural isomers and their bridged variants have been extensively explored to afford a whole class of porphyrin constitutional isomers.…”

Section: Introductionmentioning

confidence: 99%

“…[16,17] Recently, a relevant molecular pattern has been identified in tetraazuliporphyrin tetracation. [17] An analogous relationship that intertwines the hypothetical [18]annulenes of C 2h or lower symmetry, the porphyrin structural isomers and their bridged variants have been extensively explored to afford a whole class of porphyrin constitutional isomers. [2,6,[18][19][20][21][22] For instance, a porphycene molecule (8) imprints an [18]annulene frame of C 2h symmetry (7).…”

Section: Introductionmentioning

confidence: 99%

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A Flexible Porphyrin–Annulene Hybrid: A Nonporphyrin Conformation formeso‐Tetraaryldivacataporphyrin

Pacholska‐Dudziak¹,

Szterenberg²,

Latos‐Grażyński³

2011

Chemistry A European J

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An annulene-porphyrin hybrid, the diaaza-deficient porphyrin 5,10,15,20-tetraaryl-21,23-divacataporphyrin, has been synthesized by an extrusion of tellurium atom(s) from 5,10,15,20-tetraaryl-21,23-ditelluraporphyrin under treatment with HCl. In addition, a monoaza-deficient 5,10,15,20-tetraaryl-21-tellura-23-vacataporphyrin was formed in the same reaction. The two new members of the vacataporphyrin family were characterized by X-ray crystallography, as well as UV/Vis and NMR spectroscopy. These aromatic molecules preserve the fundamental structural and spectroscopic features of the parent tetraarylporphyrin. The X-ray crystal structures of 21,23-divacataporphyrin and 21-tellura-23-vacataporphyrin show typical porphyrin patterns. The molecules are not strictly planar and show distortion of the annulene moieties. The N22⋅⋅⋅N24 distances (5.23 and 5.09 Å) are considerably longer than in regular porphyrins. For 21,23-divacataporphyrin, variable-temperature (1)H NMR spectroscopy data allowed the identification of divacataporphyrin stereoisomers differentiated by the geometry of the butadiene bridges. The forms remain in thermodynamic equilibrium.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Flexible Porphyrin–Annulene Hybrid: A Nonporphyrin Conformation formeso‐Tetraaryldivacataporphyrin

Pacholska‐Dudziak¹,

Szterenberg²,

Latos‐Grażyński³

2011

Chemistry A European J

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“…[14,15] Previously,w es howedt hat tetraazuliporphyrinogen 1 can be oxidized to the tetraazuliporphyrin tetracation 2,p roviding the first example of at etracarbaporphyrinoid(1.1.1.1). [16] The unique feature of 2 was the observed concentration of positive charge on the meso positions, which resulted in uniquer eactivity and spectroscopic properties. In contrast, the dications of dithia-and dioxadiazuliporphyrins 5a-b, [11,12] showed the prevalence of tropylium-like charged istribution, which is required for achieving macrocyclica romaticity.F urthermore, in contrast to 2,f or which no neutralo xidation level could be detected, diazuliporphyrins 4a-b could be synthesized by chemical reductiono f5a-b (Scheme1).…”

Section: Introductionmentioning

confidence: 99%

Carbocations Confined in a Thiatriazuliporphyrin Frame

Sprutta

Wełnic

Białek

et al. 2016

Chemistry A European J

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In the search for tricarbaporphyrinoids, a three-component acid-catalyzed condensation of azulene, 2,5-bis[(p-tolyl)hydroxymethyl]thiophene, and an aryl aldehyde has been elaborated, affording the appropriate thiatriazuliporphyrinogens. The subsequent oxidation yielded a rare example of a macrocyclic organic tetracation, which can be readily and reversibly converted into macrocyclic tri- and dicarbocations by addition of one or two hydroxides bound at the meso position(s). Further insight into the influence of carbocation formation on the geometry, electronic structure, and magnetic manifestation in (1) H NMR spectroscopy has been obtained by using density functional theory calculations. The charge distribution was evaluated by mapping electron density surfaces with electrostatic potential (ESP).

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“…In summary, the newly designed azacalixphyrin 2 a novel isostructural and isoelectronic "pyrrol-free" analogue of porphyrins [15] was easily prepared in two straightforward steps. The synthetic accessibility-based on a new strategy-is highly versatile because of the nature of the intermediates 7 and 8 for which substituents on the peripheral nitrogen atoms will be easily introduced and varied for tuning the properties of the macrocycles (solubility, geometry, donor/acceptor capability).…”

Section: Methodsmentioning

confidence: 99%