Molecular engineering of confined space in metal–organic cages

Lewis, Jack

doi:10.1039/d2cc05560k

Cited by 33 publications

(11 citation statements)

References 112 publications

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“…Poly-[n]-catenanes [1][2][3][4] self-assembled interlocked metal organic cages (MOCs) 5 are classified as mechanically interlocked materials (MIMs) and are receiving considerable interest not only due to their potential applications but also due to their aesthetic synthetic aspects. Despite advances in the synthesis of catenanes 6 , the formation of catenanes made of interlocked MOCs is still very challenging 7 .…”

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confidence: 99%

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Martí‐Rujas

Elli

Famulari

2023

Sci Rep

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Here, we show that in a supramolecular system with more than 20 building blocks forming large icosahedral M12L8 metal–organic cages (MOCs), using the instant synthesis method, it is possible to kinetically trap and control the formation of interlocking M12L8 nanocages, giving rare M12L8 TPB-ZnI2 poly-[n]-catenane. The catenanes are obtained in a one-pot reaction, selectively as amorphous (a1) or crystalline states, as demonstrated by powder X-ray diffraction (powder XRD), thermogravimetric (TG) analysis and 1H NMR. The 300 K M12L8 poly-[n]-catenane single crystal X-ray diffraction (SC-XRD) structure including nitrobenzene (1) indicates strong guest binding with the large M12L8 cage (i.e., internal volume ca. 2600 Å3), allowing its structural resolution. Conversely, slow self-assembly (5 days) leads to a mixture of the M12L8 poly-[n]-catenane and a new TPB-ZnI2 (2) coordination polymer (i.e., thermodynamic product), as revealed by SC-XRD. The neat grinding solid-state synthesis also yields amorphous M12L8 poly-[n]-catenane (a1′), but not coordination polymers, selectively in 15 min. The dynamic behavior of the M12L8 poly-[n]-catenanes demonstrated by the amorphous-to-crystalline transformation upon the uptake of ortho-, meta- and para-xylenes shows the potential of M12L8 poly-[n]-catenanes as functional materials in molecular separation. Finally, combining SC-XRD of 1 and DFT calculations specific for the solid-state, the role of the guests in the stability of the 1D chains of M12L8 nanocages is reported. Energy interactions such as interaction energies (E), lattice energies (E*), host–guest energies (Ehost-guest) and guest-guest energies (Eguest-guest) were analysed considering the X-ray structure with and without the nitrobenzene guest. Not only the synthetic control achieved in the synthesis of the M12L8 MOCs but also their dynamic behavior either in the crystalline or amorphous phase are sufficient to raise scientific interest in areas ranging from fundamental to applied sides of chemistry and material sciences.

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confidence: 99%

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Martí‐Rujas

Elli

Famulari

2023

Sci Rep

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“…Although factors such as cavity volume, 79,80 ligand-guest interactions, 55 host asymmetry 35 and metal-metal distance 19 all play a role in the host-guest chemistry of M 2 L 4 coordination cages, our work exemplies how maximising their axial helicity correlates with an exceptionally tight and adaptable binding pocket with a strong affinity toward a range of anionic guests. We anticipate this work will inspire further research into guest recognition/separation by tightly-wrapped helical cage compounds.…”

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confidence: 94%

Maximized axial helicity in a Pd₂L₄cage: inverse guest size-dependent compression and mesocate isomerism

et al. 2023

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“…Poly-[n]-catenanes 1,2,3,4 self-assembled of interlocked metal organic cages (MOCs) 5 are classi ed as mechanically interlocked materials (MIMs) and are receiving considerable interest not only due to their potential applications, but also due to their aesthetic synthetic aspects. Despite the advances in the synthesis of catenanes 6 , the formation of catenanes made of interlocked MOCs is still very challenging.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Trapping of 2,4,6-Tris(4-pyridyl)benzene and ZnI 2 into M 12 L 8 poly-[n]-catenanes using unconventional self-assembling processes

Rujas

Famulari

2023

Preprint

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Here we show that in a supramolecular system with more than 20 building blocks forming the large icosahedral M12L8 metal-organic cages (MOCs), using the instant synthesis method it is possible to kinetically trap, and control the formation of interlocking M12L8 nanocages, giving the rare M12L8 TPB-ZnI2 poly-[n]-catenane. The catenanes are obtained in one-pot reaction, selectively as amorphous (a1) or crystalline states as demonstrated by powder X-ray diffraction (powder XRD), thermogravimetrical (TG) analysis and 1H NMR. The 300 K M12L8 poly-[n]-catenane single crystal X-ray diffraction (SC-XRD) structure including nitrobenzene (1), indicates a strong guest binding with the large M12L8 cage (i.e., internal volume ca. 2700 Å3) allowing its structural resolution. Conversely, slow self-assembly (5 days) leads a mixture of the M12L8 poly-[n]-catenane and a new TPB-ZnI2 (2) coordination polymer (i.e., thermodynamic product) as revealed by SC-XRD. The neat grinding solid-state synthesis also yields the amorphous M12L8 poly-[n]-catenane (a2), but not coordination polymers, selectively in 15 mins. The dynamic behavior of the M12L8 poly-[n]-catenanes demonstrated by the amorphous-to-crystalline transformation upon the uptake of ortho-, meta- and para-xylenes, shows the potential of M12L8 poly-[n]-catenanes as functional materials in molecular separation. Finally, combining SC-XRD of 1 and DFT calculations specific for the solid-state, the role of the guests in the stability of the 1D chains of M12L8 nanocages are reported. Energy interactions such as interaction energies (E), the lattice energies (E*), the host-guest energies (Ehost-guest) and the guest-guest energies (Eguest-guest) have been analysed considering the X-ray structure with and without nitrobenzene guest. Not only the synthetic control achieved in the synthesis of the M12L8 MOCs, but also their dynamic behavior either in the crystalline or amorphous phase, are sufficient to raise the scientific interest in areas ranging from fundamental to the applied sides of chemistry and material sciences.

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Molecular engineering of confined space in metal–organic cages

Abstract: The host–guest chemistry of metal–organic cages can be modified through tailoring of structural aspects such as size, shape and functionality. In this review, strategies, opportunities and challenges of such molecular engineering are discussed.

Cited by 33 publications

References 112 publications

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Maximized axial helicity in a Pd₂L₄cage: inverse guest size-dependent compression and mesocate isomerism

Kinetic Trapping of 2,4,6-Tris(4-pyridyl)benzene and ZnI 2 into M 12 L 8 poly-[n]-catenanes using unconventional self-assembling processes

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Molecular engineering of confined space in metal–organic cages

Abstract: The host–guest chemistry of metal–organic cages can be modified through tailoring of structural aspects such as size, shape and functionality. In this review, strategies, opportunities and challenges of such molecular engineering are discussed.

Cited by 33 publications

References 112 publications

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes

Maximized axial helicity in a Pd2L4cage: inverse guest size-dependent compression and mesocate isomerism

Kinetic Trapping of 2,4,6-Tris(4-pyridyl)benzene and ZnI 2 into M 12 L 8 poly-[n]-catenanes using unconventional self-assembling processes

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Maximized axial helicity in a Pd₂L₄cage: inverse guest size-dependent compression and mesocate isomerism