An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions

Ekaterina A. Zhigileva; Yulia Yu Enakieva; Anna A. Sinelshchikova; Vladimir V. Chernyshev; Ivan N. Senchikhin; Konstantin A. Kovalenko; Irina A. Stenina; Andrey B. Yaroslavtsev; Yulia G. Gorbunova; Aslan Yu Tsivadze

doi:10.1039/d3dt01118f

An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions

Ekaterina A. Zhigileva, Yulia Yu Enakieva^*, Anna A. Sinelshchikova, Vladimir V. Chernyshev, Ivan N. Senchikhin, Konstantin A. Kovalenko, Irina A. Stenina, Andrey B. Yaroslavtsev, Yulia G. Gorbunova, Aslan Yu Tsivadze

^*Corresponding author for this work

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

2 Citations (Scopus)

Abstract

Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(ii) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10⁻³ S cm⁻¹ at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.

Original language	English
Pages (from-to)	8237-8246
Number of pages	10
Journal	Dalton Transactions
Volume	52
Issue number	24
DOIs	https://doi.org/10.1039/d3dt01118f
Publication status	Published - 17 May 2023
Externally published	Yes

Funding

The authors thank the grant (RSF No. 23-23-00516) for financial support. We are grateful to Prof. Andrey A. Shiryaev for the assistance with VT-PXRD measurements, to Prof. Mikhail S. Grigoriev for the helpful discussion about SCXRD experiments. The synthesis of precursors was supported by the Ministry of Science and Higher Education of the Russian Federation. MALDI TOF MS, NMR, IR, XPS, TGA, SEM, EDX, X-Ray and PXRD diffraction measurements along with the proton conductivity experiments were performed at the CKP FMI of the Frumkin Institute of Physical Chemistry and Electrochemistry, RAS, and using the equipment of the JRC PMR IGIC RAS. An analysis of the porous structure was carried out at the Shared Facility Centre of the Nikolaev Institute of Inorganic Chemistry, Siberian Branch, RAS. The authors acknowledge partial support from the User Facilities Center of Moscow State University.

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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Zhigileva, E. A., Enakieva, Y. Y., Sinelshchikova, A. A., Chernyshev, V. V., Senchikhin, I. N., Kovalenko, K. A., Stenina, I. A., Yaroslavtsev, A. B., Gorbunova, Y. G., & Tsivadze, A. Y. (2023). An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions. Dalton Transactions, 52(24), 8237-8246. https://doi.org/10.1039/d3dt01118f

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title = "An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions",

abstract = "Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(ii) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10−3 S cm−1 at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.",

author = "Zhigileva, {Ekaterina A.} and Enakieva, {Yulia Yu} and Sinelshchikova, {Anna A.} and Chernyshev, {Vladimir V.} and Senchikhin, {Ivan N.} and Kovalenko, {Konstantin A.} and Stenina, {Irina A.} and Yaroslavtsev, {Andrey B.} and Gorbunova, {Yulia G.} and Tsivadze, {Aslan Yu}",

note = "Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry",

year = "2023",

month = may,

day = "17",

doi = "10.1039/d3dt01118f",

language = "English",

volume = "52",

pages = "8237--8246",

journal = "Dalton Transactions",

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Zhigileva, EA, Enakieva, YY, Sinelshchikova, AA, Chernyshev, VV, Senchikhin, IN, Kovalenko, KA, Stenina, IA, Yaroslavtsev, AB, Gorbunova, YG & Tsivadze, AY 2023, 'An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions', Dalton Transactions, vol. 52, no. 24, pp. 8237-8246. https://doi.org/10.1039/d3dt01118f

TY - JOUR

T1 - An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework

T2 - optimization of proton conductivity through the exchange of counterions

AU - Zhigileva, Ekaterina A.

AU - Enakieva, Yulia Yu

AU - Sinelshchikova, Anna A.

AU - Chernyshev, Vladimir V.

AU - Senchikhin, Ivan N.

AU - Kovalenko, Konstantin A.

AU - Stenina, Irina A.

AU - Yaroslavtsev, Andrey B.

AU - Gorbunova, Yulia G.

AU - Tsivadze, Aslan Yu

PY - 2023/5/17

Y1 - 2023/5/17

N2 - Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(ii) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10−3 S cm−1 at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.

AB - Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(ii) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10−3 S cm−1 at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.

UR - http://www.scopus.com/inward/record.url?scp=85161587367&partnerID=8YFLogxK

U2 - 10.1039/d3dt01118f

DO - 10.1039/d3dt01118f

M3 - Article

C2 - 37249348

AN - SCOPUS:85161587367

SN - 1477-9226

VL - 52

SP - 8237

EP - 8246

JO - Dalton Transactions

JF - Dalton Transactions

IS - 24

ER -

An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions

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