A new one-dimensional hybrid iodoplumbate, namely, 4,4′-(anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1- pyridinium) lead iodide C30H22N2Pb2I6 (AEPyPbI), is reported here for the first time with its complete characterization. The material exhibits remarkable thermal stability (up to 300 °C), and it is unreactive under ambient conditions toward water and atmospheric oxygen, due to the quaternary nature of the nitrogen atoms present in the organic cation. The cation exhibits strong visible fluorescence under ultraviolet (UV) irradiation, and when its iodide is combined with PbI2, it forms AEPyPb2I6, an efficient light-emitting material, with a photoluminescence emission intensity comparable to that of high-quality InP epilayers. The structure determination was obtained using three-dimensional electron diffraction, and the material was extensively studied by using a wide range of techniques, such as X-ray powder diffraction, diffuse reflectance UV−visible spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, Raman and infrared spectroscopies, and photoluminescence spectroscopy. The emissive properties of the material were correlated with its electronic structure by using state-of-the-art theoretical calculations. The complex, highly conjugated electronic structure of the cation interacts strongly with that of the Pb−I network, giving rise to the peculiar optoelectronic properties of AEPyPb2I6. The material, considering its relatively easy synthesis and stability, shows promise for lightemitting and photovoltaic devices. The use of highly conjugated quaternary ammonium cations may be useful for the development of new hybrid iodoplumbates and perovskites with optoelectronic properties tailored for specific applications.

4,4′-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) Lead Iodide C30H22N2Pb2I6: A Highly Luminescent, Chemically and Thermally Stable One-Dimensional Hybrid Iodoplumbate / Romagnoli, L.; D'Annibale, A.; Blundo, E.; Patra, A.; Polimeni, A.; Meggiolaro, D.; Andrusenko, I.; Marchetti, D.; Gemmi, M.; Latini, A.. - In: CHEMISTRY OF MATERIALS. - ISSN 0897-4756. - 35:4(2023), pp. 1818-1826. [10.1021/acs.chemmater.2c03798]

4,4′-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) Lead Iodide C30H22N2Pb2I6: A Highly Luminescent, Chemically and Thermally Stable One-Dimensional Hybrid Iodoplumbate

D'Annibale A.
Secondo
Membro del Collaboration Group
;
Blundo E.
Writing – Review & Editing
;
Patra A.
Membro del Collaboration Group
;
Polimeni A.
Membro del Collaboration Group
;
Latini A.
Ultimo
Writing – Original Draft Preparation
2023

Abstract

A new one-dimensional hybrid iodoplumbate, namely, 4,4′-(anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1- pyridinium) lead iodide C30H22N2Pb2I6 (AEPyPbI), is reported here for the first time with its complete characterization. The material exhibits remarkable thermal stability (up to 300 °C), and it is unreactive under ambient conditions toward water and atmospheric oxygen, due to the quaternary nature of the nitrogen atoms present in the organic cation. The cation exhibits strong visible fluorescence under ultraviolet (UV) irradiation, and when its iodide is combined with PbI2, it forms AEPyPb2I6, an efficient light-emitting material, with a photoluminescence emission intensity comparable to that of high-quality InP epilayers. The structure determination was obtained using three-dimensional electron diffraction, and the material was extensively studied by using a wide range of techniques, such as X-ray powder diffraction, diffuse reflectance UV−visible spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, Raman and infrared spectroscopies, and photoluminescence spectroscopy. The emissive properties of the material were correlated with its electronic structure by using state-of-the-art theoretical calculations. The complex, highly conjugated electronic structure of the cation interacts strongly with that of the Pb−I network, giving rise to the peculiar optoelectronic properties of AEPyPb2I6. The material, considering its relatively easy synthesis and stability, shows promise for lightemitting and photovoltaic devices. The use of highly conjugated quaternary ammonium cations may be useful for the development of new hybrid iodoplumbates and perovskites with optoelectronic properties tailored for specific applications.
2023
hybrid perovskites; photoluminescence; crystal structure
01 Pubblicazione su rivista::01a Articolo in rivista
4,4′-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) Lead Iodide C30H22N2Pb2I6: A Highly Luminescent, Chemically and Thermally Stable One-Dimensional Hybrid Iodoplumbate / Romagnoli, L.; D'Annibale, A.; Blundo, E.; Patra, A.; Polimeni, A.; Meggiolaro, D.; Andrusenko, I.; Marchetti, D.; Gemmi, M.; Latini, A.. - In: CHEMISTRY OF MATERIALS. - ISSN 0897-4756. - 35:4(2023), pp. 1818-1826. [10.1021/acs.chemmater.2c03798]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1673589
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