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Title: Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals

Abstract

We report syntheses, crystal and electronic structures, and characterization of three new hybrid organic–inorganic halides (R)ZnBr 3(DMSO), (R) 2CdBr 4·DMSO, and (R)CdI 3(DMSO) (where (R) = C 6(CH 3) 5CH 2N(CH 3) 3, and DMSO = dimethyl sulfoxide). The compounds can be conveniently prepared as single crystals and bulk polycrystalline powders using a DMSO–methanol solvent system. On the basis of the single-crystal X-ray diffraction results carried out at room temperature and 100 K, all compounds have zero-dimensional (0D) crystal structures featuring alternating layers of bulky organic cations and molecular inorganic anions based on a tetrahedral coordination around group 12 metal cations. The presence of discrete molecular building blocks in the 0D structures results in localized charges and tunable room-temperature light emission, including white light for (R)ZnBr 3(DMSO), bluish-white light for (R) 2CdBr 4·DMSO, and green for (R)CdI 3(DMSO). The highest photoluminescence quantum yield (PLQY) value of 3.07% was measured for (R)ZnBr 3(DMSO), which emits cold white light based on the calculated correlated color temperature (CCT) of 11,044 K. All compounds exhibit fast photoluminescence lifetimes on the timescale of tens of nanoseconds, consistent with the fast luminescence decay observed in π-conjugated organic molecules. Temperature dependence photoluminescence study showed the appearance ofmore » additional peaks around 550 nm, resulting from the organic salt emission. Density functional theory calculations show that the incorporation of both the low-gap aromatic molecule R and the relatively electropositive Zn and Cd metals can lead to exciton localization at the aromatic molecular cations, which act as luminescence centers.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [3];  [4];  [1];  [1]; ORCiD logo [5];  [6];  [6]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [1]
  1. Univ. of Oklahoma, Norman, OK (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); East China Normal Univ. (ECNU), Shanghai (China)
  3. Beihang Univ., Beijing (China)
  4. Univ. of Tennessee, Knoxville, TN (United States)
  5. East China Normal Univ. (ECNU), Shanghai (China)
  6. Univ. Paris-Saclay, Versailles (France)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1489084
Alternate Identifier(s):
OSTI ID: 1490568
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 3; Journal Issue: 12; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Roccanova, Rachel, Houck, Matthew, Yangui, Aymen, Han, Dan, Shi, Hongliang, Wu, Yuntao, Glatzhofer, Daniel T., Powell, Douglas R., Chen, Shiyou, Fourati, Houcem, Lusson, Alain, Boukheddaden, Kamel, Du, Mao-Hua, and Saparov, Bayrammurad. Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals. United States: N. p., 2018. Web. doi:10.1021/acsomega.8b02883.
Roccanova, Rachel, Houck, Matthew, Yangui, Aymen, Han, Dan, Shi, Hongliang, Wu, Yuntao, Glatzhofer, Daniel T., Powell, Douglas R., Chen, Shiyou, Fourati, Houcem, Lusson, Alain, Boukheddaden, Kamel, Du, Mao-Hua, & Saparov, Bayrammurad. Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals. United States. doi:10.1021/acsomega.8b02883.
Roccanova, Rachel, Houck, Matthew, Yangui, Aymen, Han, Dan, Shi, Hongliang, Wu, Yuntao, Glatzhofer, Daniel T., Powell, Douglas R., Chen, Shiyou, Fourati, Houcem, Lusson, Alain, Boukheddaden, Kamel, Du, Mao-Hua, and Saparov, Bayrammurad. Fri . "Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals". United States. doi:10.1021/acsomega.8b02883.
@article{osti_1489084,
title = {Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals},
author = {Roccanova, Rachel and Houck, Matthew and Yangui, Aymen and Han, Dan and Shi, Hongliang and Wu, Yuntao and Glatzhofer, Daniel T. and Powell, Douglas R. and Chen, Shiyou and Fourati, Houcem and Lusson, Alain and Boukheddaden, Kamel and Du, Mao-Hua and Saparov, Bayrammurad},
abstractNote = {We report syntheses, crystal and electronic structures, and characterization of three new hybrid organic–inorganic halides (R)ZnBr3(DMSO), (R)2CdBr4·DMSO, and (R)CdI3(DMSO) (where (R) = C6(CH3)5CH2N(CH3)3, and DMSO = dimethyl sulfoxide). The compounds can be conveniently prepared as single crystals and bulk polycrystalline powders using a DMSO–methanol solvent system. On the basis of the single-crystal X-ray diffraction results carried out at room temperature and 100 K, all compounds have zero-dimensional (0D) crystal structures featuring alternating layers of bulky organic cations and molecular inorganic anions based on a tetrahedral coordination around group 12 metal cations. The presence of discrete molecular building blocks in the 0D structures results in localized charges and tunable room-temperature light emission, including white light for (R)ZnBr3(DMSO), bluish-white light for (R)2CdBr4·DMSO, and green for (R)CdI3(DMSO). The highest photoluminescence quantum yield (PLQY) value of 3.07% was measured for (R)ZnBr3(DMSO), which emits cold white light based on the calculated correlated color temperature (CCT) of 11,044 K. All compounds exhibit fast photoluminescence lifetimes on the timescale of tens of nanoseconds, consistent with the fast luminescence decay observed in π-conjugated organic molecules. Temperature dependence photoluminescence study showed the appearance of additional peaks around 550 nm, resulting from the organic salt emission. Density functional theory calculations show that the incorporation of both the low-gap aromatic molecule R and the relatively electropositive Zn and Cd metals can lead to exciton localization at the aromatic molecular cations, which act as luminescence centers.},
doi = {10.1021/acsomega.8b02883},
journal = {ACS Omega},
number = 12,
volume = 3,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsomega.8b02883

Citation Metrics:
Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: (a−c) Crystal structures and close-up views of the coordination polyhedra in (a) (R)ZnBr3(DMSO), (b) (R)2CdBr4· DMSO, and (c) (R)CdI3(DMSO). Blue and cyan tetrahedra represent coordination environments around Zn and Cd, respectively. Burgundy, purple, red, yellow, black, and light blue spheres represent Br, I, O, S, C, and N,more » respectively. For clarity, hydrogen atoms were omitted, and only a fraction of organic cations and solvent molecules are shown.« less

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