Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites

Ruyan Zhao; Randy P. Sabatini; Tong Zhu; Sasa Wang; Amin Morteza Najjarian; Andrew Johnston; Alan J. Lough; Sjoerd Hoogland; Edward H. Sargent; Dwight S. Seferos

doi:10.1021/jacs.1c09515

Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites

Ruyan Zhao, Randy P. Sabatini, Tong Zhu, Sasa Wang, Amin Morteza Najjarian, Andrew Johnston, Alan J. Lough, Sjoerd Hoogland, Edward H. Sargent, Dwight S. Seferos^*

^*Corresponding author for this work

Chemistry

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

55 Scopus citations

Abstract

Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-πinteraction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

Original language	English (US)
Pages (from-to)	19901-19908
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	143
Issue number	47
DOIs	https://doi.org/10.1021/jacs.1c09515
State	Published - Dec 1 2021

Funding

The authors thank Dr. Yangfan Xu for help with the SEM measurements. This work was supported by the University of Toronto, the Natural Sciences and Engineering Research Council, Huawei Technologies Canada Co., Ltd., and the Ontario Research Fund. Computations were performed on the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, Ontario Research Fund \u2013 Research Excellence, and the University of Toronto. D.S.S. is grateful to the Connaught Foundation for the McLean Award and NSERC for the E. W. R. Steacie Memorial Fellowship.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites",

abstract = "Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-πinteraction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.",

author = "Ruyan Zhao and Sabatini, {Randy P.} and Tong Zhu and Sasa Wang and {Morteza Najjarian}, Amin and Andrew Johnston and Lough, {Alan J.} and Sjoerd Hoogland and Sargent, {Edward H.} and Seferos, {Dwight S.}",

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AU - Zhao, Ruyan

AU - Sabatini, Randy P.

AU - Zhu, Tong

AU - Wang, Sasa

AU - Morteza Najjarian, Amin

AU - Johnston, Andrew

AU - Lough, Alan J.

AU - Hoogland, Sjoerd

AU - Sargent, Edward H.

AU - Seferos, Dwight S.

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N2 - Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-πinteraction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

AB - Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-πinteraction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

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Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites

Abstract

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