Theoretical study on electronic spectrum properties of group 12 bis-metal (II) complexes of [26]hexaphyrin(1.1.1.1.1.1)

Sun, Gang; Liu, Hongli; Jiang, Song; Wang, Xue; Liu, Chang; Fu, Qiang

doi:10.1016/j.comptc.2011.08.006

Cited by 5 publications

(1 citation statement)

References 41 publications

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“…[28]Hexaphyrin monophosphorus complex 324a and [30]hexaphyrin diphosphorus complex 325a were also found to be optically separated as a pair of examples for Möbius aromatic and Möbius antiaromatic species (Figure ). As highlighted above, the chiroptical properties of expanded porphyrins have been interesting subjects for both experimental and theoretical studies. − Combined with the detailed computational analysis, further elaboration to unveil the electronic properties of expanded porphyrins may find applications in due course.…”

Section: Applications Of Expanded Porphyrinsmentioning

confidence: 99%

Chemistry ofmeso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist

2016

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Since the discovery of its facile synthesis in 2001, meso-aryl-substituted expanded porphyrins have been developed as a new class of azaannulenes in light of their facile redox interconversions, conformational flexibilities involving flipping of the constitutional pyrroles, rich metal coordination behaviors, unprecedented chemical reactivities, effective platforms to realize versatile electronic states including Möbius aromatic and antiaromatic species, and abilities to stabilize organic radicals. In this Review, the syntheses, structures, and optical, electronic, and magnetic properties of meso-aryl-substituted expanded porphyrins and their metal complexes have been updated with a particular focus on the relationship between "aromaticity and molecular twist (molecular topology)". While the importance of the interplay of these two characteristics has been long recognized from the theoretical viewpoint, meso-aryl-substituted expanded porphyrins offered solid experimental evidence to provide Möbius aromatic and antiaromatic molecules with distinct diatropic and paratropic ring currents, respectively. This attribute is not shared with β-alkylated expanded porphyrin counterparts, underlining the importance and uniqueness of meso-aryl-substituted expanded porphyrins.

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Section: Applications Of Expanded Porphyrinsmentioning

confidence: 99%

Chemistry ofmeso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist

2016

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Theoretical investigation of the aromaticity and electronic properties of protonated and unprotonated molecules in the series hexaphyrin(1.0.0.1.0.0) to hexaphyrin(1.1.1.1.1.1)

Sun

Duan

2015

J Mol Model

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A series of hexaphyrins with different meso-carbon atoms and their protonated structures were investigated using density functional theory (DFT) and time-dependent DFT. Frontier molecular orbitals (FMOs), aromaticity, and electronic spectra were investigated systematically before and after protonation. The FMO energy gaps before and after protonation were different for the antiaromatic molecules, while they were only slightly different for the aromatic molecules. By analyzing the electronic spectra of the aromatic molecules, the absorption peaks in the Q-like and B-like bands were not significantly different before and after protonation. However, the absorption peaks of the antiaromatic molecules were clearly different before and after protonation in both the Q-like and B-like bands. [24]Hexaphyrin (1.0.1.0.1.0) has 24 π-electrons and is Hückel antiaromatic. However, the absorption spectrum of protonated [24]hexaphyrin (1.0.1.0.1.0) showed aromaticity. In addition, these conclusions were generally consistent with the FMOs, nucleus-independent chemical shifts, harmonic oscillator model of aromaticity, and absorption spectra. Although protonated [24]hexaphyrin (1.0.1.0.1.0) has 24 π-electrons and is Hückel antiaromatic, it has Möbius aromaticity because of the single-sided Möbius topological structure. This explains why [24]hexaphyrin (1.0.1.0.1.0) has diatropic ring currents in solvent. To the best of our knowledge, this system is the smallest Möbius aromatic molecule among the many uncoordinated extended porphyrins.

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Theoretical investigation of structure diversity and electronic properties in the series isomeric [26]hexaphyrin (1.1.1.1.1.1) and [28]hexaphyrin (1.1.1.1.1.1)

Sun

Lei

Liu

et al. 2016

Computational and Theoretical Chemistry

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Theoretical study on electronic spectrum properties of group 12 bis-metal (II) complexes of [26]hexaphyrin(1.1.1.1.1.1)

Cited by 5 publications

References 41 publications

Chemistry ofmeso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist

Chemistry ofmeso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist

Theoretical investigation of the aromaticity and electronic properties of protonated and unprotonated molecules in the series hexaphyrin(1.0.0.1.0.0) to hexaphyrin(1.1.1.1.1.1)

Theoretical investigation of structure diversity and electronic properties in the series isomeric [26]hexaphyrin (1.1.1.1.1.1) and [28]hexaphyrin (1.1.1.1.1.1)

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