Recent Advances of Biphenylene: Synthesis, Reactions and Uses

Takano, Hideaki; Ito, T.; Kanyiva, Kyalo Stephen; Shibata, Takanori

doi:10.1002/ejoc.201900111

Cited by 44 publications

(29 citation statements)

References 96 publications

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“…Using the VIST method, it is the purpose of this work to illustrate the concept of Baird aromaticity in a class of PAHs based on the biphenylene motif (see Figure 2). Recently, the biphenylene unit [44] has been considered for molecular conductance [8] and singlet fission [33]. Computational studies on the biphenylene unit integrated into larger PAHs have highlighted its effect on Baird aromaticity [45] and biradical character [46].…”

Section: Introductionmentioning

confidence: 99%

Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Plasser

2021

Chemistry

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Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four biphenylene-derived PAHs finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). The results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

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Section: Introductionmentioning

confidence: 99%

Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Plasser

2021

Chemistry

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show abstract

“…2). Recently, the biphenylene unit [40] has been considered for molecular conductance [8] and singlet fission [33]. Computational studies on the biphenylene unit integrated into larger PAHs have highlighted its effect on Baird aromaticity [41] and biradical character [42].…”

Section: Introductionmentioning

confidence: 99%

Exploitation of Baird Aromaticity and Clar's Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Plasser

2021

Preprint

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Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four PAHs based on the biphenylene motif finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). These results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

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“…Biphenylene and its derivatives offer many applications such as thin films polymer with anomalously high electrical conductivity [17], and the precursor for 2D porous graphene dehydrogenation or biphenylene carbon with intrinsic nonzero gap value and delocalized frontier orbitals that indicate a structure with high electronic mobility [18]. A recent study by Takano et al [19] shows that biphenylene motif can be used in functional materials, namely, it can act as a spacer in a variety of functional molecules and serves as a backbone for catalysts and ligands. Recently, Pagano et al [20] reported that actinide substitution into one of the benzene rings of the biphenylene produces a new, more stable electronic structure whose usefulness led to energy storage applications.…”

Section: Introductionmentioning

confidence: 99%

Analysis of Biphenylene and Benzo{3,4}cyclobuta{1,2-c}thiophene Molecular Orbital Structure using the Huckel Method

Anggraini¹,

Sutjahja²

2021

Rev. Chim.

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The Huckel method is an old fashion method to predict the molecular orbital and energies of  electrons in a conjugated molecule. Although Huckel`s theory`s approximations are relatively crude, its general results are still reasonable compared to the advanced computing method and experimental results for many molecules. This paper describes the Huckel calculation of biphenylene and benzo{3,4}cyclobuta{1,2-c}thiophene using the HuLis software. The benzo{3,4}cyclobuta{1,2-c}thiophene is a derivative of biphenylene, in which case one of the benzene rings is replaced by a thiophene ring. This change produces new electronic properties that are interesting to study. This work focused on calculating those molecules on energy levels diagrams, linear combination coefficient of molecular orbitals, molecular orbital shape, energy gap, resonance energy, bond-order, bond length, and charge distribution (π electron population). Besides, we calculate the harmonic oscillator measure of aromaticity (HOMA) parameter to study the Huckel method`s validity.

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Recent Advances of Biphenylene: Synthesis, Reactions and Uses

Cited by 44 publications

References 96 publications

Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Exploitation of Baird Aromaticity and Clar's Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Analysis of Biphenylene and Benzo{3,4}cyclobuta{1,2-c}thiophene Molecular Orbital Structure using the Huckel Method

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