Sn4-δB12Se12[Qx], Q = Se, Te, a B12Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

Daniel G. Chica; Ioannis Spanopoulos; Shiqiang Hao; Chris Wolverton; Mercouri G. Kanatzidis

doi:10.1021/acs.chemmater.0c04503

Sn_4-δB₁₂Se₁₂[Q_x], Q = Se, Te, a B₁₂Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

Daniel G. Chica, Ioannis Spanopoulos, Shiqiang Hao, Chris Wolverton, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

We report the open framework semiconductor, Sn4B12Se12, synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B12Se12]14- anion assembled into a 3D tunnel structure with open tunnels and is chemically stable over a wide pH range from concentrated nitric acid to 3 M NaOH aqueous solution. The rigid nature of this structure and high chemical stability allows chemical strategies for the removal of Se chains from the tunnels, giving an empty tunnel structure and subsequent insertion of tellurium chains as confirmed through single-crystal X-ray diffraction. The as-synthesized Sn4B12Se12[Se3.80] contains selenium chains in the tunnels and crystallizes in the hexagonal space group P6322 with a = b = 13.5927(7) Å, c = 9.8167(5) Å. After removal of Se and subsequent Te insertion, the space group remains the same with small changes in lattice parameters and occupancy of tin sites. The experimentally obtained optical band gap of the as-synthesized material is 1.66 eV and can be modulated by chemical modifications. DFT calculations of the empty framework show an indirect nature of the band gap calculated at 1.16 eV. The neutral framework of Sn4B12Se12 is a new example of a microporous semiconductor with exceptional stability and electronic properties that stem from the presence of icosahedral boron clusters.

Original language	English (US)
Pages (from-to)	1723-1730
Number of pages	8
Journal	Chemistry of Materials
Volume	33
Issue number	5
DOIs	https://doi.org/10.1021/acs.chemmater.0c04503
State	Published - Mar 9 2021

Funding

This work was supported by the National Science Foundation through Grant DMR-2003476. This work made use of the IMSERC X-RAY facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), and Northwestern University. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), Northwestern’s MRSEC program (NSF DMR-1720139), the Keck foundation, and the State of Illinois through IIN.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.0c04503

Cite this

@article{86b98bf42c904dfdaa8d3cc34b1b8374,

title = "Sn4-δB12Se12[Qx], Q = Se, Te, a B12Cluster Tunnel Framework Hosting Neutral Chalcogen Chains",

abstract = "We report the open framework semiconductor, Sn4B12Se12, synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B12Se12]14- anion assembled into a 3D tunnel structure with open tunnels and is chemically stable over a wide pH range from concentrated nitric acid to 3 M NaOH aqueous solution. The rigid nature of this structure and high chemical stability allows chemical strategies for the removal of Se chains from the tunnels, giving an empty tunnel structure and subsequent insertion of tellurium chains as confirmed through single-crystal X-ray diffraction. The as-synthesized Sn4B12Se12[Se3.80] contains selenium chains in the tunnels and crystallizes in the hexagonal space group P6322 with a = b = 13.5927(7) {\AA}, c = 9.8167(5) {\AA}. After removal of Se and subsequent Te insertion, the space group remains the same with small changes in lattice parameters and occupancy of tin sites. The experimentally obtained optical band gap of the as-synthesized material is 1.66 eV and can be modulated by chemical modifications. DFT calculations of the empty framework show an indirect nature of the band gap calculated at 1.16 eV. The neutral framework of Sn4B12Se12 is a new example of a microporous semiconductor with exceptional stability and electronic properties that stem from the presence of icosahedral boron clusters.",

author = "Chica, {Daniel G.} and Ioannis Spanopoulos and Shiqiang Hao and Chris Wolverton and Kanatzidis, {Mercouri G.}",

note = "Funding Information: This work was supported by the National Science Foundation through Grant DMR-2003476. This work made use of the IMSERC X-RAY facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), and Northwestern University. This work made use of the EPIC facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), Northwestern{\textquoteright}s MRSEC program (NSF DMR-1720139), the Keck foundation, and the State of Illinois through IIN. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = mar,

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doi = "10.1021/acs.chemmater.0c04503",

language = "English (US)",

volume = "33",

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publisher = "American Chemical Society",

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T1 - Sn4-δB12Se12[Qx], Q = Se, Te, a B12Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

AU - Chica, Daniel G.

AU - Spanopoulos, Ioannis

AU - Hao, Shiqiang

AU - Wolverton, Chris

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: This work was supported by the National Science Foundation through Grant DMR-2003476. This work made use of the IMSERC X-RAY facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), and Northwestern University. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), Northwestern’s MRSEC program (NSF DMR-1720139), the Keck foundation, and the State of Illinois through IIN. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/3/9

Y1 - 2021/3/9

N2 - We report the open framework semiconductor, Sn4B12Se12, synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B12Se12]14- anion assembled into a 3D tunnel structure with open tunnels and is chemically stable over a wide pH range from concentrated nitric acid to 3 M NaOH aqueous solution. The rigid nature of this structure and high chemical stability allows chemical strategies for the removal of Se chains from the tunnels, giving an empty tunnel structure and subsequent insertion of tellurium chains as confirmed through single-crystal X-ray diffraction. The as-synthesized Sn4B12Se12[Se3.80] contains selenium chains in the tunnels and crystallizes in the hexagonal space group P6322 with a = b = 13.5927(7) Å, c = 9.8167(5) Å. After removal of Se and subsequent Te insertion, the space group remains the same with small changes in lattice parameters and occupancy of tin sites. The experimentally obtained optical band gap of the as-synthesized material is 1.66 eV and can be modulated by chemical modifications. DFT calculations of the empty framework show an indirect nature of the band gap calculated at 1.16 eV. The neutral framework of Sn4B12Se12 is a new example of a microporous semiconductor with exceptional stability and electronic properties that stem from the presence of icosahedral boron clusters.

AB - We report the open framework semiconductor, Sn4B12Se12, synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B12Se12]14- anion assembled into a 3D tunnel structure with open tunnels and is chemically stable over a wide pH range from concentrated nitric acid to 3 M NaOH aqueous solution. The rigid nature of this structure and high chemical stability allows chemical strategies for the removal of Se chains from the tunnels, giving an empty tunnel structure and subsequent insertion of tellurium chains as confirmed through single-crystal X-ray diffraction. The as-synthesized Sn4B12Se12[Se3.80] contains selenium chains in the tunnels and crystallizes in the hexagonal space group P6322 with a = b = 13.5927(7) Å, c = 9.8167(5) Å. After removal of Se and subsequent Te insertion, the space group remains the same with small changes in lattice parameters and occupancy of tin sites. The experimentally obtained optical band gap of the as-synthesized material is 1.66 eV and can be modulated by chemical modifications. DFT calculations of the empty framework show an indirect nature of the band gap calculated at 1.16 eV. The neutral framework of Sn4B12Se12 is a new example of a microporous semiconductor with exceptional stability and electronic properties that stem from the presence of icosahedral boron clusters.

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