Octaethyltetraoxaporphyrin Dication—Counterpart of Octaethylporphyrin in the Tetraoxaporphyrin Series

Vogel, Emanuel; Dörr, Joachim; Herrmann, Adalbert; Lex, Johann; Schmickler, Hans; Walgenbach, Peter; Gisselbrecht, Jean Paul; Gross, M.L.

doi:10.1002/anie.199315971

Cited by 29 publications

(16 citation statements)

References 26 publications

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“…When the inner‐N atoms are replaced by the inner‐O atoms, in comparison with the inner‐N atoms, the inner‐O atoms are much more harder to join into the conjugated system, driving the ring current away to the outer skeleton and changing the former aromatic 18 π‐electron porphyrin macrocycle into an anti‐aromatic 20 π‐electron porphyrinoid one 7 . [ 21 ] Due to the perfect 20 π‐electron current ring pathway shown in Figure , the LLDP is as strong as −22.2 a.u., which is even stronger than the values of −19.8 and −14.4 a.u. for 1 .…”

Section: Resultsmentioning

confidence: 99%

An Overall Comprehension of Anti‐Aromatic Porphyrinoids Using 3D‐Graphical Chemical Shielding Description

Jiang

2020

Advcd Theory and Sims

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A systematic investigation to rank the anti-aromatic porphyrinoids is performed. Based on density functional theory calculations, four rules are summarized to obtain the highest anti-aromatic porphyrinoids: 1) the replacement from meso-C to meso-(─C≡C─), 2) the replacement from pyrrole unit to inner-N to inner-O, 3) the replacement from two opposite meso-C/N atoms to two pyrrole units, and 4) the replacement from one pyrrole ring to a carbonyl benzene ring. It is worth noting that the long chain with alternating single/double bonds is not beneficial or harmful to the anti-aromaticity.

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Section: Resultsmentioning

confidence: 99%

An Overall Comprehension of Anti‐Aromatic Porphyrinoids Using 3D‐Graphical Chemical Shielding Description

Jiang

2020

Advcd Theory and Sims

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“…The discovery of TOPs also opens the door to synthesize other porphyrin-like tetrafuran macrocycles [2−4]. For these reasons, various spectroscopic experiments have been conducted to study the ground and excited state properties of TOPs [1][2][3][4][5][6]11]. The dicationic TOP 2+ is the isoelectronic analogue of normal closed-shell metalloporphyrins (MPs), and it shares many similarities in UV-visible absorption spectra with MPs [1,6,11].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Resonance Raman Spectra of Tetraoxaporphyrin Dication by TDDFT Calculation

Wang

Hongwei

Zhang

et al. 2015

Chinese Journal of Chemical Physics

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The B state excited resonance Raman scattering of tetraoxaporphyrin dication (TOP 2+) was theoretically studied with DFT/TDDFT calculations and the sum-overstates approach of polarizability including both the A and B terms contributions. The resonance Raman spectra calculated with PBE1PBE, B3LYP, Cam-B3LYP, and B3LYP-D3 functionals are similar to each other in general, with PBE1PBE and B3LYP being better in reproducing resonance Raman intensities in comparison with the experiment. The calculated relative intensities of the totally symmetric modes are excellently consistent with the experiment. The TDDFT calculations manifested a considerable deformation of the B state along the ν 2 , ν 6 , ν 7 , and ν 8 modes, which is responsible for the strong resonance Raman intensities of these modes. The resonance Raman intensities of non-totally symmetric modes were calculated to be weaker than the totally symmetric modes by one or two order of magnitude, which qualitatively agrees with the experiment. However, the resonance Raman intensity of the ν 10 mode (C β C β stretch, B 1g symmetry) predicted by TDDFT calculations is unexpectedly small whereas that of the ν 11 mode (symmetric C α C m stretch, B 1g symmetry) is too large, which is assumed to be caused by the Jahn-Teller instability for the B state of TOP 2+ .

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“…14,16 Further, examples involving the use of dialkyl acetylenes as dienophiles are extremely rare. 17 Scheme 2 General approach to maleic anhydrides from alkynes Attractive as this strategy is, the lack of practical methods for converting furans into maleic anhydrides is not to be overlooked (cf. B → A, Scheme 2).…”

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Expedient Assembly of Bioactive Maleic Anhydrides Using Click Diels–Alder Chemistry

Boukouvalas

Thibault

Loach

2014

Synlett

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A versatile pathway to substituted maleic anhydrides is illustrated by the synthesis of the nanomolar FTase inhibitor chaetomellic anhydride A, a germination promoter, and a novel bisanhydride cross-linking reagent for cell or tissue fixation. Starting from commercial or easily prepared alkynes, these targets were assembled in two steps by click-unclick oxazole-alkyne cycloaddition-cycloreversion and furan oxyfunctionalization.

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Octaethyltetraoxaporphyrin Dication—Counterpart of Octaethylporphyrin in the Tetraoxaporphyrin Series

Abstract: geometry of the copper complex (Fig. 3a).ii3f Moreover. the EPR spectrum is indicative of a type-I1 copper binding site in a similar ligdnd environment with g , , = 2.27 and A , , = 173 (cm-x lo4). Peisach and Blumberg analysis[141 is

Cited by 29 publications

References 26 publications

An Overall Comprehension of Anti‐Aromatic Porphyrinoids Using 3D‐Graphical Chemical Shielding Description

An Overall Comprehension of Anti‐Aromatic Porphyrinoids Using 3D‐Graphical Chemical Shielding Description

Theoretical Study on Resonance Raman Spectra of Tetraoxaporphyrin Dication by TDDFT Calculation

Expedient Assembly of Bioactive Maleic Anhydrides Using Click Diels–Alder Chemistry

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