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Title: Bulk assembly of organic metal halide nanotubes

Abstract

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C6H13N4)3Pb2Br7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb2Br95–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C6H13N4+). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.

Authors:
 [1];  [1];  [2]; ORCiD logo [2];  [2];  [3];  [2];  [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [3]
  1. FAMU-FSU College of Engineering, Tallahassee, FL (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. FAMU-FSU College of Engineering, Tallahassee, FL (United States); Florida State Univ., Tallahassee, FL (United States)
  4. Univ. of Florida, Gainesville, FL (United States)
  5. 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
OSTI Identifier:
1410201
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 12; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, and Ma, Biwu. Bulk assembly of organic metal halide nanotubes. United States: N. p., 2017. Web. doi:10.1039/c7sc03675b.
Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, & Ma, Biwu. Bulk assembly of organic metal halide nanotubes. United States. https://doi.org/10.1039/c7sc03675b
Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, and Ma, Biwu. 2017. "Bulk assembly of organic metal halide nanotubes". United States. https://doi.org/10.1039/c7sc03675b. https://www.osti.gov/servlets/purl/1410201.
@article{osti_1410201,
title = {Bulk assembly of organic metal halide nanotubes},
author = {Lin, Haoran and Zhou, Chenkun and Tian, Yu and Besara, Tiglet and Neu, Jennifer and Siegrist, Theo and Zhou, Yan and Bullock, James and Schanze, Kirk S. and Ming, Wenmei and Du, Mao -Hua and Ma, Biwu},
abstractNote = {The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C6H13N4)3Pb2Br7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb2Br95–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C6H13N4+). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.},
doi = {10.1039/c7sc03675b},
url = {https://www.osti.gov/biblio/1410201}, journal = {Chemical Science},
issn = {2041-6520},
number = 12,
volume = 8,
place = {United States},
year = {Mon Oct 16 00:00:00 EDT 2017},
month = {Mon Oct 16 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 60 works
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Figures / Tables:

Fig. 1 Fig. 1: (a) View of the structure of (HMTA)3Pb2Br7 (red: lead atoms; green: bromine atoms; blue: nitrogen atoms; gray: carbon atoms; purple polyhedra: PbBr6 octahedra and Pb2Br9 dimers; hydrogen atoms are hidden for clarity). (b) Side view of an individual lead bromide nanotube. (c) Side view of an individual leadmore » bromide nanotube surrounded by organic cations. (d) Ball-and-stick model of an individual HMTA unit (hydrogen atoms are omitted). (e) Ball-and-stick model of an individual face-sharing lead bromide dimer Pb2Br9 with detailed bond lengths and bond angles listed in the ESI.† (f) Top view of a rugged ring formed by six lead bromide dimers. (g) Top view of a rugged metal halide ring coated with organic cations inside and outside.« less

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Works referencing / citing this record:

Microwave Absorption of Organic Metal Halide Nanotubes
journal, December 2019


Bulk Assembly of Corrugated 1D Metal Halides with Broadband Yellow Emission
journal, December 2018


Spintronics of Hybrid Organic–Inorganic Perovskites: Miraculous Basis of Integrated Optoelectronic Devices
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Negative Thermal Quenching of Efficient White‐Light Emission in a 1D Ladder‐Like Organic/Inorganic Hybrid Material
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Intrinsic White‐Light‐Emitting Metal–Organic Frameworks with Structurally Deformable Secondary Building Units
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Intrinsic White-Light-Emitting Metal-Organic Frameworks with Structurally Deformable Secondary Building Units
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Semiconducting crystalline inorganic–organic hybrid metal halide nanochains
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White light emission in low-dimensional perovskites
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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.