Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

doi:10.1021/acs.chemmater.8b00129

Title: Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

Abstract

Here, we report the synthesis and characterization of (Ph ₄P) ₂SbCl ₅, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph ₄P ₊) and antimony (Sb ³⁺) chloride salts, (Ph ₄P) ₂SbCl ₅ bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl ₅ ^2– with strong excited-state structural distortion. Interestingly, (Ph ₄P) ₂SbCl ₅ bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.

Authors:

Zhou, Chenkun ^[1]; Worku, Michael ^[2]; Neu, Jennifer ^[3]; Lin, Haoran ^[1]; Tian, Yu ^[2]; Lee, Sujin ^[1]; Zhou, Yan ^[4];

^[5];

^[6]; Hao, Ayou ^[7]; Djurovich, Peter I. ^[8]; Siegrist, Theo ^[9];

^[10];

^[11]

Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering
Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices; East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
East China Normal Univ. (ECNU), Shanghai (China). Key Lab. of Polar Materials and Devices; East China Normal Univ. (ECNU), Shanghai (China). Dept. of Physics
Florida State Univ., Tallahassee, FL (United States). High-Performance Materials Institute (HPMI)
Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering; Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Florida Agricultural and Mechanical Univ. and Florida State Univ. (FAMU-FSU), Tallahassee, FL (United States). College of Engineering, Dept. of Chemical and Biomedical Engineering; Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program; Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry

Publication Date:: 2018-03-12

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); National Science Foundation (NSF)

OSTI Identifier:: 1435249

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 30; Journal Issue: 7; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.chemmater.8b00129.

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                    Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, & Ma, Biwu. Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency.  United States.  doi:10.1021/acs.chemmater.8b00129.

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                    Zhou, Chenkun, Worku, Michael, Neu, Jennifer, Lin, Haoran, Tian, Yu, Lee, Sujin, Zhou, Yan, Han, Dan, Chen, Shiyou, Hao, Ayou, Djurovich, Peter I., Siegrist, Theo, Du, Mao-Hua, and Ma, Biwu. Mon .  
        "Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency".  United States.  doi:10.1021/acs.chemmater.8b00129.  https://www.osti.gov/servlets/purl/1435249.

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@article{osti_1435249,

  title        = {Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency},

  author       = {Zhou, Chenkun and Worku, Michael and Neu, Jennifer and Lin, Haoran and Tian, Yu and Lee, Sujin and Zhou, Yan and Han, Dan and Chen, Shiyou and Hao, Ayou and Djurovich, Peter I. and Siegrist, Theo and Du, Mao-Hua and Ma, Biwu},

  abstractNote = {Here, we report the synthesis and characterization of (Ph4P)2SbCl5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph4P+) and antimony (Sb3+) chloride salts, (Ph4P)2SbCl5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl52– with strong excited-state structural distortion. Interestingly, (Ph4P)2SbCl5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.},

  doi          = {10.1021/acs.chemmater.8b00129},

  journal      = {Chemistry of Materials},

  number       = 7,

  volume       = 30,

  place        = {United States},

  year         = {2018},

  month        = {3}

}

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Journal Article:

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DOI: 10.1021/acs.chemmater.8b00129

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Cited by: 9 works

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Figures / Tables:

Figure 1: a) View of the structure of (Ph₄P)₂SbCl₅ (red spheres: antimony atoms; blue spheres: chloride atoms; orange spheres: nitrogen atoms; gray spheres: carbon atoms; red polyhedra: SbCl₅^2-; hydrogen atoms are hidden for clarity). b) View of an individual SbCl₅^2- anion and nearest neighbor Ph₄P⁺ cations.

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Works referencing / citing this record:

CCDC 1813002: Experimental Crystal Structure Determination: KEZGOO : bis(tetraphenylphosphonium) pentachloro-antimony
dataset, December 2017

Zhou, Chenkun; Worku, Michael; Neu, Jennifer
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1yvky9

Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission
journal, February 2019

Gautier, Romain; Massuyeau, Florian; Galnon, Gabin
Advanced Materials, Vol. 31, Issue 14
DOI: 10.1002/adma.201807383

Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides
journal, July 2018

Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia
Angewandte Chemie International Edition, Vol. 57, Issue 35
DOI: 10.1002/anie.201806452

Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019

Dehnhardt, Natalie; Böth, André; Heine, Johanna
Dalton Transactions, Vol. 48, Issue 16
DOI: 10.1039/c9dt00575g

Organic cation directed hybrid lead halides of zero-dimensional to two-dimensional structures with tunable photoluminescence properties
journal, January 2019

Yue, Cheng-Yang; Sun, Hai-Xiao; Liu, Quan-Xiu
Inorganic Chemistry Frontiers, Vol. 6, Issue 10
DOI: 10.1039/c9qi00684b

Enhancing the phosphorescence of hybrid metal halides through molecular sensitization
journal, January 2019

Gong, Liao-Kuo; Li, Jian-Rong; Wu, Zhao-Feng
Journal of Materials Chemistry C, Vol. 7, Issue 32
DOI: 10.1039/c9tc03067k

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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Title: Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

Abstract

Citation Formats

Figures / Tables:

CCDC 1813002: Experimental Crystal Structure Determination: KEZGOO : bis(tetraphenylphosphonium) pentachloro-antimony dataset, December 2017

Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission journal, February 2019

Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides journal, July 2018

Surprising discoveries on the way to an old compound: four transient iodido antimonates journal, January 2019

Organic cation directed hybrid lead halides of zero-dimensional to two-dimensional structures with tunable photoluminescence properties journal, January 2019

Enhancing the phosphorescence of hybrid metal halides through molecular sensitization journal, January 2019

CCDC 1813002: Experimental Crystal Structure Determination: KEZGOO : bis(tetraphenylphosphonium) pentachloro-antimony
dataset, December 2017

Lead Halide Post‐Perovskite‐Type Chains for High‐Efficiency White‐Light Emission
journal, February 2019

Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides
journal, July 2018

Surprising discoveries on the way to an old compound: four transient iodido antimonates
journal, January 2019

Organic cation directed hybrid lead halides of zero-dimensional to two-dimensional structures with tunable photoluminescence properties
journal, January 2019

Enhancing the phosphorescence of hybrid metal halides through molecular sensitization
journal, January 2019