Three-dimensional chiral metal-organic frameworks: synthesis and structure transformation

Three-dimensional chiral metal-organic frameworks: synthesis and structure transformation Full article

Journal

Nanomaterials
ISSN: 2079-4991

Output data

Year: 2026, Volume: 16, Number: 1, Article number : 22, Pages count : 12 DOI: 10.3390/nano16010022

Tags

metal–organic framework; chiral coordination polymers; structural transformation; benzene and cyclohexane separation

Authors

Dubskikh Vadim A. ¹ , Lysova Anna A. ¹ , Samsonenko Denis G. ¹ , Kovalenko Konstantin A. ¹ , Dybtsev Danil N. ¹ , Fedin Vladimir P. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., Novosibirsk 630090, Russia

Four new porous homochiral metal–organic frameworks (MOFs), [M2(camph)2(bpa)]∙Solv (M = Co(II), Ni(II), Cu(II) and Zn(II)), based on (+)-camphoric acid (H2camph) and 1,2-bis(4-pyridyl)ethane (bpa) were synthesized and characterized. The crystal structures of [Ni2(camph)2(bpa)] and [Zn2(camph)2(bpa)] were established by single-crystal X-ray diffraction analysis. Powder X-ray data prove the phase purity and isostructural nature of all four compounds. The thermal stability of [M2(camph)2(bpa)] was found to depend on the electronic configuration, as well as on the redox properties of the metal cation, and varied from 225 °C (M = Zn2+) to 375 °C (M = Ni2+). The reversible, solvent-induced sponge-like dynamics of the coordination frameworks was thoroughly investigated. Changes in the positions of reflexes, related to the length of the flexible bpa linker, were observed by powder XRD, pointing to transitions between an open-framework phase and a squeezed, non-porous phase in a crystal-to-crystal manner, while the integrity and connectivity of the coordination network were maintained. Size-selective adsorption from a benzene–cyclohexane 1:1 mixture on [Zn2(camph)2(bpa)] was studied by 1H NMR analysis. The benzene-favorable composition of guest molecules (C6H6:C6H12 = 5:1) occluded within the host crystalline sponge revealed a preferable adsorption affinity towards smaller benzene compared with larger cyclohexane. High framework stability in various solvents, as well as successful molecular separation in the liquid state, validates the potential utilization of chiral porous metal(II) camphorate MOFs in important stereoselective applications.

Dubskikh V.A. , Lysova A.A. , Samsonenko D.G. , Kovalenko K.A. , Dybtsev D.N. , Fedin V.P.
Three-dimensional chiral metal-organic frameworks: synthesis and structure transformation
Nanomaterials. 2026. V.16. N1. 22 :1-12. DOI: 10.3390/nano16010022

Submitted:	Dec 2, 2025
Published print:	Jan 7, 2026

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