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Heterotrimetallic Double Cavity Cages: Syntheses and Selective Guest Binding.

ABSTRACT: A strategy for the generation of heterotrimetallic double cavity (DC) cages [Pd_n Pt_m L₄ ]⁶⁺ (DC1: n=1, m=2; and DC2: n=2, m=1) is reported. The DC cages were generated by combining an inert platinum(II) tetrapyridylaldehyde complex with a suitably substituted pyridylamine and Pd^II ions. ¹ H and DOSY nuclear magnetic resonance spectroscopy (NMR) and electrospray ionization mass spectrometry (ESIMS) data were consistent with the formation of the DC architectures. DC1 and DC2 were shown to interact with several different guest molecules. The structure of DC1, which features two identical cavities, binding two 2,6-diaminoanthraquinone (DAQ) guest molecules was determined by single-crystal X-ray crystallography. In addition, DC1 was shown to bind two molecules of 5-fluorouracil (5-FU) in a statistical (non-cooperative) manner. In contrast, DC2, which features two different cage cavities, was found to interact with two different guests, 5-FU and cisplatin, selectively.

SUBMITTER: Lisboa LS

PROVIDER: S-EPMC9310627 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Allosteric Guest Binding in Chiral Zirconium(IV) Double Decker Porphyrin Cages.

Project description:Chiral zirconium(IV) double cage sandwich complex Zr(1)2 has been synthesized in one step from porphyrin cage H21. Zr(1)2 was obtained as a racemate, which was resolved by HPLC and the enantiomers were isolated in >99.5 % ee. Their absolute configurations were assigned on the basis of X-ray crystallography and circular dichroism spectroscopy. Vibrational circular dichroism (VCD) experiments on the enantiomers of Zr(1)2 revealed that the chirality around the zirconium center is propagated throughout the whole cage structure. The axial conformational chirality of the double cage complex displayed a VCD fingerprint similar to the one observed previously for a related chiral cage compound with planar and point chirality. Zr(1)2 shows fluorescence, which is quenched when viologen guests bind in its cavities. The binding of viologen and dihydroxybenzene derivatives in the two cavities of Zr(1)2 occurs with negative allostery, the cooperativity factors α (=4 K2/K1) being as low as 0.0076 for the binding of N,N'-dimethylviologen. These allosteric effects are attributed to a pinching of the second cavity as a result of guest binding in the first cavity.

| S-EPMC7898692 | biostudies-literature

Purely Covalent Molecular Cages and Containers for Guest Encapsulation.

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Absolute configuration and host-guest binding of chiral porphyrin-cages by a combined chiroptical and theoretical approach.

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Chiral Self-Discrimination and Guest Recognition in Helicene-Based Coordination Cages.

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| S-EPMC6996569 | biostudies-literature

Capture of Singlet Oxygen Modulates Host-Guest Behavior of Coordination Cages.

Project description:The anthracene panels of two tetrahedral MII 4 L6 cages, where MII =CoII or FeII , were found to react with photogenerated singlet oxygen (1 O2 ) in a hetero-Diels-Alder reaction. ESI-MS analysis showed the cobalt(II) cages to undergo complete transformation of all anthracene panels into endoperoxides, whereas the iron(II) congeners underwent incomplete conversion. The reaction was found to be partially reversible in the case of the 1-FeII cage. The dioxygen-cage cycloadducts were found to bind a set of guest molecules more weakly than the parent cages, with affinity dropping by more than two orders of magnitude in some cases. The light-driven cycloaddition reaction between cage and 1 O2 thus served as a stimulus for guest release and reuptake.

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| S-EPMC7383889 | biostudies-literature

Theoretical Investigation of the Fusion Process of Mono-Cages to Tri-Cages with CH4/C2H6 Guest Molecules in sI Hydrates.

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| S-EPMC8659103 | biostudies-literature

Shape-selective crystallisation of fluxional carbon cages.

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