Metal-organic Kagome lattices M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M = Ni and Cu): From semiconducting to metallic by metal substitution

Shuang Chen; Jun Dai; Xiao Cheng Zeng

doi:10.1039/c4cp05328a

Metal-organic Kagome lattices M₃(2,3,6,7,10,11-hexaiminotriphenylene)₂ (M = Ni and Cu): From semiconducting to metallic by metal substitution

Shuang Chen, Jun Dai, Xiao Cheng Zeng^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

130 Citations (Scopus)

38 Downloads (CityUHK Scholars)

Abstract

Motivated by recent experimental synthesis of a semiconducting metal-organic graphene analogue (J. Am. Chem. Soc., 2014, 136, 8859), i.e., Ni₃ (2,3,6,7,10,11 hexaiminotriphenylene)₂ [Ni₃(HITP)₂], a new Kagome lattice, Cu₃(HITP)₂, is designed by substituting the coordination of Ni by Cu. Such substitution results in interesting changes in electronic properties of the M3(HITP)₂ bulk and two-dimensional (2D) sheets. In Ni₃(HITP)₂, each Ni atom adopts the dsp² hybridization, forming a perfect 2D conjugation, whereas in Cu₃(HITP)₂, each Cu atom adopts the sp³ hybridization, resulting in a distorted 2D sheet. The M₃(HITP)₂ bulks, assembled from M₃(HITP)₂ sheets via both strong p-p interaction and weak metal-metal interaction, are metallic. However, the 2D Ni₃(HITP)₂ sheet is a semiconductor with a narrow band gap whereas the 2D Cu₃(HITP)₂ sheet is a metal. Remarkably, both the 2D M₃(HITP)₂ Kagome lattices possess Dirac bands in the vicinity of the Fermi level. Additional ab initio molecular dynamics simulations show that both sheets exhibit high thermal stability at elevated temperatures. Our theoretical study offers new insights into tunability of electronic properties for the 2D metal-organic frameworks (MOFs).

Original language	English
Pages (from-to)	5954-5958
Journal	Physical Chemistry Chemical Physics
Volume	17
Issue number	8
DOIs	https://doi.org/10.1039/c4cp05328a
Publication status	Published - Feb 2015
Externally published	Yes

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@article{469ce8abac7d4e6096441d4f18f2624f,

title = "Metal-organic Kagome lattices M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M = Ni and Cu): From semiconducting to metallic by metal substitution",

abstract = "Motivated by recent experimental synthesis of a semiconducting metal-organic graphene analogue (J. Am. Chem. Soc., 2014, 136, 8859), i.e., Ni3 (2,3,6,7,10,11 hexaiminotriphenylene)2 [Ni3(HITP)2], a new Kagome lattice, Cu3(HITP)2, is designed by substituting the coordination of Ni by Cu. Such substitution results in interesting changes in electronic properties of the M3(HITP)2 bulk and two-dimensional (2D) sheets. In Ni3(HITP)2, each Ni atom adopts the dsp2 hybridization, forming a perfect 2D conjugation, whereas in Cu3(HITP)2, each Cu atom adopts the sp3 hybridization, resulting in a distorted 2D sheet. The M3(HITP)2 bulks, assembled from M3(HITP)2 sheets via both strong p-p interaction and weak metal-metal interaction, are metallic. However, the 2D Ni3(HITP)2 sheet is a semiconductor with a narrow band gap whereas the 2D Cu3(HITP)2 sheet is a metal. Remarkably, both the 2D M3(HITP)2 Kagome lattices possess Dirac bands in the vicinity of the Fermi level. Additional ab initio molecular dynamics simulations show that both sheets exhibit high thermal stability at elevated temperatures. Our theoretical study offers new insights into tunability of electronic properties for the 2D metal-organic frameworks (MOFs).",

author = "Shuang Chen and Jun Dai and Zeng, {Xiao Cheng}",

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Metal-organic Kagome lattices M₃(2,3,6,7,10,11-hexaiminotriphenylene)₂ (M = Ni and Cu): From semiconducting to metallic by metal substitution. / Chen, Shuang; Dai, Jun; Zeng, Xiao Cheng.
In: Physical Chemistry Chemical Physics, Vol. 17, No. 8, 02.2015, p. 5954-5958.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

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AU - Dai, Jun

AU - Zeng, Xiao Cheng

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

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N2 - Motivated by recent experimental synthesis of a semiconducting metal-organic graphene analogue (J. Am. Chem. Soc., 2014, 136, 8859), i.e., Ni3 (2,3,6,7,10,11 hexaiminotriphenylene)2 [Ni3(HITP)2], a new Kagome lattice, Cu3(HITP)2, is designed by substituting the coordination of Ni by Cu. Such substitution results in interesting changes in electronic properties of the M3(HITP)2 bulk and two-dimensional (2D) sheets. In Ni3(HITP)2, each Ni atom adopts the dsp2 hybridization, forming a perfect 2D conjugation, whereas in Cu3(HITP)2, each Cu atom adopts the sp3 hybridization, resulting in a distorted 2D sheet. The M3(HITP)2 bulks, assembled from M3(HITP)2 sheets via both strong p-p interaction and weak metal-metal interaction, are metallic. However, the 2D Ni3(HITP)2 sheet is a semiconductor with a narrow band gap whereas the 2D Cu3(HITP)2 sheet is a metal. Remarkably, both the 2D M3(HITP)2 Kagome lattices possess Dirac bands in the vicinity of the Fermi level. Additional ab initio molecular dynamics simulations show that both sheets exhibit high thermal stability at elevated temperatures. Our theoretical study offers new insights into tunability of electronic properties for the 2D metal-organic frameworks (MOFs).

AB - Motivated by recent experimental synthesis of a semiconducting metal-organic graphene analogue (J. Am. Chem. Soc., 2014, 136, 8859), i.e., Ni3 (2,3,6,7,10,11 hexaiminotriphenylene)2 [Ni3(HITP)2], a new Kagome lattice, Cu3(HITP)2, is designed by substituting the coordination of Ni by Cu. Such substitution results in interesting changes in electronic properties of the M3(HITP)2 bulk and two-dimensional (2D) sheets. In Ni3(HITP)2, each Ni atom adopts the dsp2 hybridization, forming a perfect 2D conjugation, whereas in Cu3(HITP)2, each Cu atom adopts the sp3 hybridization, resulting in a distorted 2D sheet. The M3(HITP)2 bulks, assembled from M3(HITP)2 sheets via both strong p-p interaction and weak metal-metal interaction, are metallic. However, the 2D Ni3(HITP)2 sheet is a semiconductor with a narrow band gap whereas the 2D Cu3(HITP)2 sheet is a metal. Remarkably, both the 2D M3(HITP)2 Kagome lattices possess Dirac bands in the vicinity of the Fermi level. Additional ab initio molecular dynamics simulations show that both sheets exhibit high thermal stability at elevated temperatures. Our theoretical study offers new insights into tunability of electronic properties for the 2D metal-organic frameworks (MOFs).

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