Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

Eugenia S. Vasileiadou; Imra S. Tajuddin; Michael C. De Siena; Vladislav V. Klepov; Mikaël Kepenekian; George Volonakis; Jacky Even; Lukasz Wojtas; Ioannis Spanopoulos; Xiuquan Zhou; Abishek K. Iyer; Julie L. Fenton; William R. Dichtel; Mercouri G. Kanatzidis

doi:10.1021/acs.chemmater.3c00164

Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

Eugenia S. Vasileiadou, Imra S. Tajuddin, Michael C. De Siena, Vladislav V. Klepov, Mikaël Kepenekian, George Volonakis, Jacky Even, Lukasz Wojtas, Ioannis Spanopoulos, Xiuquan Zhou, Abishek K. Iyer, Julie L. Fenton, William R. Dichtel, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

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

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Abstract

The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et₆)₃Pb₁₁X₃₁ (X = I, Br), where T is 1,3,5-tris-(4-aminophenyl)benzene. The materials are synthesized through an in situ N-alkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et₆)₃Pb₁₁X₃₁ consist of an unprecedented Ia3̅ framework of [Pb₁₁X₃₁]^9- one-dimensional (1D) chains embedded with (T-Et₆)³⁺ cations, affording an overall 3D topology. The constituent [Pb₁₁X₃₁]^9- chains include exclusively octahedral lead halide units with clusters of face- and edge-sharing connectivity, giving rise to weak broad emission centered at ∼660 nm observed at 78 K. (T-Et₆)₃Pb₁₁I₃₁ demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T₇Pb₃Br₂₇·DMF and T₂Sn₃Br₁₈·4H₂O·0.5Br₂, both of which feature blue PL emission at room temperature.

Original language	English (US)
Pages (from-to)	5267-5280
Number of pages	14
Journal	Chemistry of Materials
Volume	35
Issue number	14
DOIs	https://doi.org/10.1021/acs.chemmater.3c00164
State	Published - Jul 25 2023

Funding

This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the grant DE-SC-0012541. E.S.V. acknowledges the Dr. John N. Nicholson fellowship through Northwestern University. A.K.I. and M.G.K. would like to acknowledge the Air Force Office of Scientific Research Grant number FA9550-18-S-0003. I.S. acknowledges support from USF startup funds. J.L.F. was supported by an Arnold O. Beckman Postdoctoral Fellowship from the Arnold and Mabel Beckman Foundation (USA). This work made use of the NUANCE Center and IMSERC facilities of Northwestern University, which have received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633). E.S.V. thanks Prof. Christos Malliakas, Prof. Ram Seshadri, Prof. Anthony Cheetham, and Prof. Michael Chabinyc for productive discussion.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.3c00164

Cite this

Vasileiadou, E. S., Tajuddin, I. S., De Siena, M. C., Klepov, V. V., Kepenekian, M., Volonakis, G., Even, J., Wojtas, L., Spanopoulos, I., Zhou, X., Iyer, A. K., Fenton, J. L., Dichtel, W. R., & Kanatzidis, M. G. (2023). Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability. Chemistry of Materials, 35(14), 5267-5280. https://doi.org/10.1021/acs.chemmater.3c00164

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title = "Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability",

abstract = "The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et6)3Pb11X31 (X = I, Br), where T is 1,3,5-tris-(4-aminophenyl)benzene. The materials are synthesized through an in situ N-alkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et6)3Pb11X31 consist of an unprecedented Ia3̅ framework of [Pb11X31]9- one-dimensional (1D) chains embedded with (T-Et6)3+ cations, affording an overall 3D topology. The constituent [Pb11X31]9- chains include exclusively octahedral lead halide units with clusters of face- and edge-sharing connectivity, giving rise to weak broad emission centered at ∼660 nm observed at 78 K. (T-Et6)3Pb11I31 demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T7Pb3Br27·DMF and T2Sn3Br18·4H2O·0.5Br2, both of which feature blue PL emission at room temperature.",

author = "Vasileiadou, \{Eugenia S.\} and Tajuddin, \{Imra S.\} and \{De Siena\}, \{Michael C.\} and Klepov, \{Vladislav V.\} and Mika{\"e}l Kepenekian and George Volonakis and Jacky Even and Lukasz Wojtas and Ioannis Spanopoulos and Xiuquan Zhou and Iyer, \{Abishek K.\} and Fenton, \{Julie L.\} and Dichtel, \{William R.\} and Kanatzidis, \{Mercouri G.\}",

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Vasileiadou, ES, Tajuddin, IS, De Siena, MC, Klepov, VV, Kepenekian, M, Volonakis, G, Even, J, Wojtas, L, Spanopoulos, I, Zhou, X, Iyer, AK, Fenton, JL, Dichtel, WR & Kanatzidis, MG 2023, 'Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability', Chemistry of Materials, vol. 35, no. 14, pp. 5267-5280. https://doi.org/10.1021/acs.chemmater.3c00164

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T1 - Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

AU - Vasileiadou, Eugenia S.

AU - Tajuddin, Imra S.

AU - De Siena, Michael C.

AU - Klepov, Vladislav V.

AU - Kepenekian, Mikaël

AU - Volonakis, George

AU - Even, Jacky

AU - Wojtas, Lukasz

AU - Spanopoulos, Ioannis

AU - Zhou, Xiuquan

AU - Iyer, Abishek K.

AU - Fenton, Julie L.

AU - Dichtel, William R.

AU - Kanatzidis, Mercouri G.

PY - 2023/7/25

Y1 - 2023/7/25

N2 - The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et6)3Pb11X31 (X = I, Br), where T is 1,3,5-tris-(4-aminophenyl)benzene. The materials are synthesized through an in situ N-alkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et6)3Pb11X31 consist of an unprecedented Ia3̅ framework of [Pb11X31]9- one-dimensional (1D) chains embedded with (T-Et6)3+ cations, affording an overall 3D topology. The constituent [Pb11X31]9- chains include exclusively octahedral lead halide units with clusters of face- and edge-sharing connectivity, giving rise to weak broad emission centered at ∼660 nm observed at 78 K. (T-Et6)3Pb11I31 demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T7Pb3Br27·DMF and T2Sn3Br18·4H2O·0.5Br2, both of which feature blue PL emission at room temperature.

AB - The limitations of three-dimensional (3D) perovskites are related to their narrow structural tunability of the organic cations and their moisture sensitivity. Herein, we report a new family of 3D cubic hybrid metal halides (T-Et6)3Pb11X31 (X = I, Br), where T is 1,3,5-tris-(4-aminophenyl)benzene. The materials are synthesized through an in situ N-alkylation of T and an efficient one-step solvothermal reaction containing ethanol, initiating a tunable synthetic avenue for the acquisition of structurally complex hybrid halides with luminophores. (T-Et6)3Pb11X31 consist of an unprecedented Ia3̅ framework of [Pb11X31]9- one-dimensional (1D) chains embedded with (T-Et6)3+ cations, affording an overall 3D topology. The constituent [Pb11X31]9- chains include exclusively octahedral lead halide units with clusters of face- and edge-sharing connectivity, giving rise to weak broad emission centered at ∼660 nm observed at 78 K. (T-Et6)3Pb11I31 demonstrates water stability for at least 7 days. Synthesis through ambient pressure results in tunable structural variations of zero-dimensional (0D) structures rendering T7Pb3Br27·DMF and T2Sn3Br18·4H2O·0.5Br2, both of which feature blue PL emission at room temperature.

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Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

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CCDC 2216514: Experimental Crystal Structure Determination

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Novel 3D Cubic Topology in Hybrid Lead Halides with a Symmetric Aromatic Triammonium Exhibiting Water Stability

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CCDC 2216514: Experimental Crystal Structure Determination

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CCDC 2216513: Experimental Crystal Structure Determination

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