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Three-Dimensional Carbon Allotropes Comprising Phenyl Rings and Acetylenic Chains in sp+sp(2) Hybrid Networks.

Wang JT, Chen C, Li HD, Mizuseki H, Kawazoe Y - Sci Rep (2016)

Bottom Line: These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp(2)-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively.Simulated phonon spectra reveal that these structures are dynamically stable.The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.

View Article: PubMed Central - PubMed

Affiliation: Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.

ABSTRACT
We here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp(2) bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp(2)-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, while phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.

No MeSH data available.


Three-dimensional carbon networks of rh6 polybenzene and polybenzene-ynes with phenylic rings and acetylenic chains in  symmetry. (a) Rh6 polybenzene in an all sp2 3D bonding network with lattice parameters a = 6.9022 Å, c = 3.470 Å, occupying the 18 h (0.8805, 0.1195, 0.5576) position, which comprises three zigzag benzene rings as its building blocks. (b) Rh12 phenylacetylene with lattice parameters a = 11.6050 Å and c = 3.6443 Å. The 18h1 (0.8579, 0.9289, 0.4849) atoms form three benzene rings and 18h2 (0.8617, 0.7233, 0.6021) atoms form nine acetylenic yne-bonds located between the benzene rings. (c) Rh18 phenyldiacetylene with lattice parameters a = 16.0963 Å and c = 4.1987 Å. The atoms on 18h1 (0.1023, 0.0511, 0.5065) site form three benzene rings; The atoms on 18h2 (0.1008, 0.8992, 0.4507) and 18h3 (0.1435, 0.8565, 0.3755) sites form nine butadiyne located between the benzene rings. The primitive cell is marked by yellow lines.
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f1: Three-dimensional carbon networks of rh6 polybenzene and polybenzene-ynes with phenylic rings and acetylenic chains in symmetry. (a) Rh6 polybenzene in an all sp2 3D bonding network with lattice parameters a = 6.9022 Å, c = 3.470 Å, occupying the 18 h (0.8805, 0.1195, 0.5576) position, which comprises three zigzag benzene rings as its building blocks. (b) Rh12 phenylacetylene with lattice parameters a = 11.6050 Å and c = 3.6443 Å. The 18h1 (0.8579, 0.9289, 0.4849) atoms form three benzene rings and 18h2 (0.8617, 0.7233, 0.6021) atoms form nine acetylenic yne-bonds located between the benzene rings. (c) Rh18 phenyldiacetylene with lattice parameters a = 16.0963 Å and c = 4.1987 Å. The atoms on 18h1 (0.1023, 0.0511, 0.5065) site form three benzene rings; The atoms on 18h2 (0.1008, 0.8992, 0.4507) and 18h3 (0.1435, 0.8565, 0.3755) sites form nine butadiyne located between the benzene rings. The primitive cell is marked by yellow lines.

Mentions: We first present the structural characterization of the simplest 3D phenylacetylene network constructed by inserting triple (–C≡C–) yne-bonds into the rh6 polybenzene lattice (see Fig. 1a), as well as the so-called 2D graphyne by inserting triple yne-bonds into an expanded graphene sheet21. This new carbon phase has a () symmetry as that of rh6 polybenzene3 and topologically corresponds to 2D γ-graphyne24. In the hexagonal representation, it has a 36-atom hexagonal unit cell (see Fig. 1b) with lattice parameters a = 11.6050 Å, c = 3.6443 Å, occupying the 18h1 (0.8579, 0.9289, 0.4849) and 18h2 (0.8617, 0.7233, 0.6021) Wyckoff positions. The carbon atoms on the 18h1 sites form three benzene rings, as in rh6 carbon, with aromatic sp2 hybridization, while the carbon atoms on the 18h2 sites form nine triple yne-bonds located between the benzene rings with an ethyne-type sp-hybridization. As in rh6 carbon3, this structure also can be regarded as a three-dimensional chiral crystalline modification of carbyne connected via zigzag benzene rings with alternating single, triple and aromatic carbon-carbon bonds. It contains three distinct carbon-carbon bond lengths, a longer bond of 1.433 Å (C1–C1) in the benzene rings and two shorter bonds of 1.389 Å (C1–C2) and 1.232 Å (C2–C2) associated with the single and triple bond in carbyne chains, respectively. Meanwhile, there are three different bond angles, 171.13° for C1–C2–C2 along the carbyne chains, 119.39° for C1–C1–C1 inside and 120.21° for C1–C1–C2 out of the zigzag benzene rings, respectively. On the other hand, in the rhombohedral representation, it has a 12-atom primitive unit cell with equilibrium lattice parameters a = 6.8094 Å, α = 116.889°, occupying the 6 h (0.3428, 0.5560, 0.5560) and 6 h (0.4638, 0.4638, 0.8788) position, thus this 3D-phenylacetylene is also termed as rh12 carbon.


Three-Dimensional Carbon Allotropes Comprising Phenyl Rings and Acetylenic Chains in sp+sp(2) Hybrid Networks.

Wang JT, Chen C, Li HD, Mizuseki H, Kawazoe Y - Sci Rep (2016)

Three-dimensional carbon networks of rh6 polybenzene and polybenzene-ynes with phenylic rings and acetylenic chains in  symmetry. (a) Rh6 polybenzene in an all sp2 3D bonding network with lattice parameters a = 6.9022 Å, c = 3.470 Å, occupying the 18 h (0.8805, 0.1195, 0.5576) position, which comprises three zigzag benzene rings as its building blocks. (b) Rh12 phenylacetylene with lattice parameters a = 11.6050 Å and c = 3.6443 Å. The 18h1 (0.8579, 0.9289, 0.4849) atoms form three benzene rings and 18h2 (0.8617, 0.7233, 0.6021) atoms form nine acetylenic yne-bonds located between the benzene rings. (c) Rh18 phenyldiacetylene with lattice parameters a = 16.0963 Å and c = 4.1987 Å. The atoms on 18h1 (0.1023, 0.0511, 0.5065) site form three benzene rings; The atoms on 18h2 (0.1008, 0.8992, 0.4507) and 18h3 (0.1435, 0.8565, 0.3755) sites form nine butadiyne located between the benzene rings. The primitive cell is marked by yellow lines.
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f1: Three-dimensional carbon networks of rh6 polybenzene and polybenzene-ynes with phenylic rings and acetylenic chains in symmetry. (a) Rh6 polybenzene in an all sp2 3D bonding network with lattice parameters a = 6.9022 Å, c = 3.470 Å, occupying the 18 h (0.8805, 0.1195, 0.5576) position, which comprises three zigzag benzene rings as its building blocks. (b) Rh12 phenylacetylene with lattice parameters a = 11.6050 Å and c = 3.6443 Å. The 18h1 (0.8579, 0.9289, 0.4849) atoms form three benzene rings and 18h2 (0.8617, 0.7233, 0.6021) atoms form nine acetylenic yne-bonds located between the benzene rings. (c) Rh18 phenyldiacetylene with lattice parameters a = 16.0963 Å and c = 4.1987 Å. The atoms on 18h1 (0.1023, 0.0511, 0.5065) site form three benzene rings; The atoms on 18h2 (0.1008, 0.8992, 0.4507) and 18h3 (0.1435, 0.8565, 0.3755) sites form nine butadiyne located between the benzene rings. The primitive cell is marked by yellow lines.
Mentions: We first present the structural characterization of the simplest 3D phenylacetylene network constructed by inserting triple (–C≡C–) yne-bonds into the rh6 polybenzene lattice (see Fig. 1a), as well as the so-called 2D graphyne by inserting triple yne-bonds into an expanded graphene sheet21. This new carbon phase has a () symmetry as that of rh6 polybenzene3 and topologically corresponds to 2D γ-graphyne24. In the hexagonal representation, it has a 36-atom hexagonal unit cell (see Fig. 1b) with lattice parameters a = 11.6050 Å, c = 3.6443 Å, occupying the 18h1 (0.8579, 0.9289, 0.4849) and 18h2 (0.8617, 0.7233, 0.6021) Wyckoff positions. The carbon atoms on the 18h1 sites form three benzene rings, as in rh6 carbon, with aromatic sp2 hybridization, while the carbon atoms on the 18h2 sites form nine triple yne-bonds located between the benzene rings with an ethyne-type sp-hybridization. As in rh6 carbon3, this structure also can be regarded as a three-dimensional chiral crystalline modification of carbyne connected via zigzag benzene rings with alternating single, triple and aromatic carbon-carbon bonds. It contains three distinct carbon-carbon bond lengths, a longer bond of 1.433 Å (C1–C1) in the benzene rings and two shorter bonds of 1.389 Å (C1–C2) and 1.232 Å (C2–C2) associated with the single and triple bond in carbyne chains, respectively. Meanwhile, there are three different bond angles, 171.13° for C1–C2–C2 along the carbyne chains, 119.39° for C1–C1–C1 inside and 120.21° for C1–C1–C2 out of the zigzag benzene rings, respectively. On the other hand, in the rhombohedral representation, it has a 12-atom primitive unit cell with equilibrium lattice parameters a = 6.8094 Å, α = 116.889°, occupying the 6 h (0.3428, 0.5560, 0.5560) and 6 h (0.4638, 0.4638, 0.8788) position, thus this 3D-phenylacetylene is also termed as rh12 carbon.

Bottom Line: These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp(2)-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively.Simulated phonon spectra reveal that these structures are dynamically stable.The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.

View Article: PubMed Central - PubMed

Affiliation: Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.

ABSTRACT
We here identify by ab initio calculations a new type of three-dimensional (3D) carbon allotropes that consist of phenyl rings connected by linear acetylenic chains in sp+sp(2) bonding networks. These structures are constructed by inserting acetylenic or diacetylenic bonds into an all sp(2)-hybridized rhombohedral polybenzene lattice, and the resulting 3D phenylacetylene and phenyldiacetylene nets comprise a 12-atom and 18-atom rhombohedral primitive unit cells in the symmetry, which are characterized as the 3D chiral crystalline modification of 2D graphyne and graphdiyne, respectively. Simulated phonon spectra reveal that these structures are dynamically stable. Electronic band calculations indicate that phenylacetylene is metallic, while phenyldiacetylene is a semiconductor with an indirect band gap of 0.58 eV. The present results establish a new type of carbon phases and offer insights into their outstanding structural and electronic properties.

No MeSH data available.