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- W4313893527 abstract "Abstract Here we show that in a supramolecular system with more than 20 building blocks forming the large icosahedral M 12 L 8 metal-organic cages ( MOCs ), using the instant synthesis method it is possible to kinetically trap , and control the formation of interlocking M 12 L 8 nanocages, giving the rare M 12 L 8 TPB-ZnI 2 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 1 H NMR. The 300 K M 12 L 8 poly-[ n ]-catenane single crystal X-ray diffraction (SC-XRD) structure including nitrobenzene ( 1 ), indicates a strong guest binding with the large M 12 L 8 cage ( i.e. , internal volume ca . 2700 Å 3 ) allowing its structural resolution. Conversely, slow self-assembly (5 days) leads a mixture of the M 12 L 8 poly-[ n ]-catenane and a new TPB-ZnI 2 ( 2 ) coordination polymer ( i.e. , thermodynamic product) as revealed by SC-XRD. The neat grinding solid-state synthesis also yields the amorphous M 12 L 8 poly-[ n ]-catenane ( a2 ), but not coordination polymers, selectively in 15 mins. The dynamic behavior of the M 12 L 8 poly-[ n ]-catenanes demonstrated by the amorphous-to-crystalline transformation upon the uptake of ortho -, meta - and para -xylenes, shows the potential of M 12 L 8 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 M 12 L 8 nanocages are reported. Energy interactions such as interaction energies ( E ), the lattice energies ( E* ), the host-guest energies ( E host-guest ) and the guest-guest energies ( E guest-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 M 12 L 8 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." @default.
- W4313893527 created "2023-01-10" @default.
- W4313893527 creator A5012343103 @default.
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- W4313893527 date "2023-01-09" @default.
- W4313893527 modified "2023-10-18" @default.
- W4313893527 title "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" @default.
- W4313893527 doi "https://doi.org/10.21203/rs.3.rs-2431653/v1" @default.
- W4313893527 hasPublicationYear "2023" @default.
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