Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C6H5(CH2)4NH3)4MX7·H2O (M = Bi, In, X = Br or I)

Da Chen; Shiqiang Hao; Liubing Fan; Yangwu Guo; Jiyong Yao; Christopher Wolverton; Mercouri G. Kanatzidis; Jing Zhao; Quanlin Liu

doi:10.1021/acs.chemmater.1c02896

Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C₆H₅(CH₂)₄NH₃)₄MX₇·H₂O (M = Bi, In, X = Br or I)

Da Chen, Shiqiang Hao, Liubing Fan, Yangwu Guo, Jiyong Yao, Christopher Wolverton, Mercouri G. Kanatzidis^*, Jing Zhao^*, Quanlin Liu

^*Corresponding author for this work

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

46 Scopus citations

Abstract

Recent discoveries in organic-inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic-inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼ ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3- (M = Bi, In, X = Br, I) and unbound X- ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3- (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.

Original language	English (US)
Pages (from-to)	8106-8111
Number of pages	6
Journal	Chemistry of Materials
Volume	33
Issue number	20
DOIs	https://doi.org/10.1021/acs.chemmater.1c02896
State	Published - Oct 26 2021

Funding

The authors thank Nengneng Luo from Guangxi University, China, for the discussion of the properties of the noncentrosymmetric compounds. This work was supported by the National Natural Science Foundation of China (51972021) and the Fundamental Research Funds for the Central Universities FRF-IDRY-19-005. M.G.K. acknowledges support from AFOSR (grant FA9550-18-S-0003, NLO properties). S.H. and C.W. (DFT calculations) acknowledge support from the Department of Energy, Office of Science Basic Energy Sciences under Grant DE-SC0014520. Access to QUEST, the supercomputing resource facilities at Northwestern University, is also acknowledged.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.1c02896

Cite this

@article{6ded97d3ae704941a6ce469122319aed,

title = "Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C6H5(CH2)4NH3)4MX7·H2O (M = Bi, In, X = Br or I)",

abstract = "Recent discoveries in organic-inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic-inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼ ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3- (M = Bi, In, X = Br, I) and unbound X- ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3- (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.",

author = "Da Chen and Shiqiang Hao and Liubing Fan and Yangwu Guo and Jiyong Yao and Christopher Wolverton and Kanatzidis, {Mercouri G.} and Jing Zhao and Quanlin Liu",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = oct,

day = "26",

doi = "10.1021/acs.chemmater.1c02896",

language = "English (US)",

volume = "33",

pages = "8106--8111",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C6H5(CH2)4NH3)4MX7·H2O (M = Bi, In, X = Br or I)

AU - Chen, Da

AU - Hao, Shiqiang

AU - Fan, Liubing

AU - Guo, Yangwu

AU - Yao, Jiyong

AU - Wolverton, Christopher

AU - Kanatzidis, Mercouri G.

AU - Zhao, Jing

AU - Liu, Quanlin

PY - 2021/10/26

Y1 - 2021/10/26

N2 - Recent discoveries in organic-inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic-inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼ ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3- (M = Bi, In, X = Br, I) and unbound X- ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3- (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.

AB - Recent discoveries in organic-inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic-inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼ ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3- (M = Bi, In, X = Br, I) and unbound X- ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3- (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.

UR - http://www.scopus.com/inward/record.url?scp=85118175645&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85118175645&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.1c02896

DO - 10.1021/acs.chemmater.1c02896

M3 - Article

AN - SCOPUS:85118175645

SN - 0897-4756

VL - 33

SP - 8106

EP - 8111

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 20

ER -

Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C₆H₅(CH₂)₄NH₃)₄MX₇·H₂O (M = Bi, In, X = Br or I)

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 2104881: Experimental Crystal Structure Determination

CCDC 2104882: Experimental Crystal Structure Determination

CCDC 2142091: Experimental Crystal Structure Determination

Cite this

Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C6H5(CH2)4NH3)4MX7·H2O (M = Bi, In, X = Br or I)

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2104881: Experimental Crystal Structure Determination

CCDC 2104882: Experimental Crystal Structure Determination

CCDC 2142091: Experimental Crystal Structure Determination

Cite this

Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C₆H₅(CH₂)₄NH₃)₄MX₇·H₂O (M = Bi, In, X = Br or I)