Virginia Guiotto¹, Maria Sole Notari², Diletta Morelli Venturi³, Alberto Ricchebuono^1*, Melissa Castagnoli², Christoph Meier³, Francesca Nardelli⁴, Lucia Calucci^4,5, Matteo Signorile^1*, Marco Taddei^6,5, Valentina Crocellà¹, Ferdinando Costantino²

1 Dipartimento di Chimica, Centro di Riferimento NIS,Unità di Ricerca INSTM, Università di Torino,Via G. Quarello 15/A and Via P. Giuria 7, I-10125 Torino, Italy

2 Dipartimento di Chimica, Biologia e Biotecnologie,Unità di Ricerca INSTM, Università di Perugia,Via Elce di Sotto 8, 06123 Perugia, Italy

3 Institut für Anorganische Chemie,Christian-Albrechts-UniversitätKiel, 24118 Kiel, Germany

4 Istituto di Chimica dei Composti Organo Metallici,Unità di Ricerca INSTM, Consiglio Nazionale delle Ricerche,Via Giuseppe Moruzzi 1, 56124 Pisa, Italy

5 Centro per l’Integrazione della Strumentazione Scientifica dell’Università di Pisa (CISUP),Lungarno Pacinotti 43/44, 56126 Pisa, Italy

6 Dipartimento di Chimica e Chimica Industriale,Unità di Ricerca INSTM, Università di Pisa,Via Giuseppe Moruzzi 13, 56124 Pisa, Italy

* Corresponding authors emails: alberto.ricchebuono@unito.it, matteo.signorile@unito.it

DOI10.24435/materialscloud:d6-dy [version v1]

Publication date: May 21, 2025

How to cite this record

Virginia Guiotto, Maria Sole Notari, Diletta Morelli Venturi, Alberto Ricchebuono, Melissa Castagnoli, Christoph Meier, Francesca Nardelli, Lucia Calucci, Matteo Signorile, Marco Taddei, Valentina Crocellà, Ferdinando Costantino, A flexible, perfluorinated analogue of aluminum fumarate metal-organic framework, Materials Cloud Archive 2025.78 (2025), https://doi.org/10.24435/materialscloud:d6-dy

Description

We report the synthesis of Al-TFS, a novel aluminum metal-organic framework (MOF) based on tetrafluorosuccinic acid (H₂TFS), of formula Al(OH)(TFS)·1.5H₂O, introducing a new member to the family of perfluorinated MOFs. The structure of the MOF, solved ab-initio from laboratory powder X-ray diffraction data, displays structural analogies with that of the commercially available Al-fumarate (Basolite A520). The structure is composed of 1D infinite OH-bridged Al octahedra chains connected by the dicarboxylic linkers, designing rhombic channels decorated by fluorine atoms. Upon water removal, the MOF undergoes a phase transition leading to a moderate expansion of the unit cell. Volumetric analysis revealed the presence of ultra-micropores with a size lower than 4 Å. Gas sorption measurements demonstrated for Al-TFS a slightly higher CO₂ selectivity compared to N₂ and CH₄ than the Al-fumarate analogue, with peculiar shapes of the isotherms suggesting a dynamic response of the framework to CO₂ adsorption. Using different complementary techniques (in situ infrared spectroscopy, powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, gas/vapor sorption), and density functional theory simulations, the flexibility of the new MOF was disclosed, highlighting the significant impact of fluorination in tailoring materials with structural flexibility and peculiar adsorption properties. This record contains the structural models for the Al-TFS (TFS = tetrafluorosuccinate) in its hydrated and dehydrated phases. IR spectra have been simulated for both structures and allowed tracking the associated phase transition via comparison with experimental results.

Materials Cloud sections using this data

Files

File name	Size	Description
INCAR_opt MD5md5:038442a49523dec15621e35754654318	457 Bytes	INCAR (VASP input file) for geometry optimization
INCAR_freq MD5md5:e88cafa0fce6287cbaab731160f67701	476 Bytes	INCAR (VASP input file) for frequency calculation
evacuated.vasp MD5md5:15fa4deffd9f79a24a50e51318773a20	6.8 KiB	Optimized structure (VASP CONTCAR format) of evacuated Al-TFS
as-synthesized.vasp MD5md5:ba9bae6a9bbf2a1fc072a9b2e82b5dd9	4.2 KiB	Optimized structure (VASP CONTCAR format) of as-synthesized Al-TFS

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External references

Keywords

MOF DFT vibrational properties phase transition