Polyoxometalate condensation and transformation mediated by adaptive coordination-assembled molecular flasks.

Here we report polyoxometalate (POM) condensation or transformation reactions mediated by adaptive coordination-assembled molecular flasks. Addition of NaSiO to the (MoO)⊂1·(NO) complex containing Lindquist-type clusters as guests leads to the formation of a new (SiMoO)⊂2·(NO) host-guest complex, where the generated Keggin-type cluster served as a trigger for the host transformation from cage 1 to isomeric bowl 2. Conversion from 1 to 2 driven by the condensation was found to be 27.

Yb-Induced Bright Ligand Up-Conversion Luminescence in 1D Coordination Polymers.

Ln-induced ligand up-conversion luminescence (UCL) in coordination polymers (CPs) effectively overcomes the inherent limitations of conventional organic UCL mechanisms. However, current research on UCL in Ln-CPs has predominantly focused on the UCL of Ln⁺ ions themselves, while investigations into Ln⁺-induced ligand UCL is overlooked in Ln-CPs. Herein, by doping Yb⁺ into the Ln-CPs of [Y(FCA)] 1) (FCA = 9-fluorenone-2-carboxylic acid), Yb-doped 1D chain Ln-CPs of [YYb(FCA)] (x = 0.

Bottom-up construction of chiral metal-peptide assemblies from metal cluster motifs.

The exploration of artificial metal-peptide assemblies (MPAs) is one of the most exciting fields because of their great potential for simulating the dynamics and functionality of natural proteins. However, unfavorable enthalpy changes make forming discrete complexes with large and adaptable cavities from flexible peptide ligands challenging. Here, we present a strategy integrating metal-cluster building blocks and peptides to create chiral metal-peptide assemblies and get a family of enantiopure [R-/S-NiL] (n = 2, 3, 6) MPAs, including the R-/S-NiL capsule, the S-NiL trigonal prism, and the R-/S-NiL octahedron cage.

Ln/Cu Bimetallic Nanoclusters with Enhanced NIR-II Luminescence.

Coinage-metal clusters with excellent luminescence properties have attracted considerable interest due to their intriguing structures and potential applications. However, achieving strong near-infrared (NIR) luminescence in these clusters is highly challenging. Here, we have successfully synthesized the first Ln/Cu bimetallic clusters, formulated as [LnCuOCl(2-MeO-PhC≡C)] (ClO) (Ln = Yb for , Er for , and Gd for ).

Strong NIR-II Magneto-Optical Activity of a Chiral SmCu Cage.

The magneto-optical response of chiral materials holds significant potential for applications in physics, chemistry, and biology. However, exploration of the near-infrared (NIR) magneto-optical response remains limited. Herein, we report the synthesis and strong NIR-II magneto-optical activity of three pairs of chiral 34 clusters of (Ln = Sm, Gd, and Dy).

From Helices to Crystals: Multiscale Representation of Chirality in Double-Helix Structures.

Single crystals with chiral shapes aroused the interest of chemists due to their fascinating polarization rotation properties. Although the formation of large-scale spiral structures is considered to be a potential factor in chiral crystals, the precise mechanism behind their formation remains elusive. Herein, we present a rare phenomenon involving the multitransfer and expression of chirality at micro-, meso-, and macroscopic levels, starting from chiral carbon atoms and extending to the double-helical secondary structure, ultimately resulting in the chiral geometry of crystals.

Guest-Driven Self-Assembly and Chiral Induction of Photofunctional Lanthanide Tetrahedral Cages.

Chiral luminescent lanthanide-organic cages have many potential applications in enantioselective recognition, sensing, and asymmetric catalysis. However, due to the paucity of structures and their limited cavities, host-guest chemistry with lanthanide-organic cages has remained elusive so far. Herein, we report a guest-driven self-assembly and chiral induction approach for the construction of otherwise inaccessible LnL-type (Ln = lanthanide ions, i.

Photooxidase Mimicking with Adaptive Coordination Molecular Capsules.

One important feature of enzyme catalysis is the induced-fit conformational change after binding substrates. Herein, we report a biomimetic water-soluble molecular capsule featuring adaptive structural change toward substrate binding, which offers an ideal platform for efficient photocatalysis. The molecular capsule was coordination-assembled from three anthracene-bridged bis-TPT [TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] ligands and six (bpy)Pd(NO) (bpy = 2,2'-bipyridine).

Hexameric Lanthanide-Organic Capsules with Tertiary Structure and Emergent Functions.

Biological macromolecules always function through a collective behavior of the aggregated constituents, which usually are self-assembled together via noncovalent interactions. Likewise, artificial supramolecular assemblies, whose properties and functions are mainly derived from their primary and secondary structures, may also aggregate into high-order architectures with emergent functions not available on the individual components. Here we report the first example of an insulin-like hexamerization of lanthanide triple helicates toward a 4 nm diameter hexameric capsule via consecutive metal-directed and anion-directed assembly processes.

Controlled Self-Assembly and Multistimuli-Responsive Interconversions of Three Conjoined Twin-Cages.

Stimuli-responsive structural transformations between discrete coordination supramolecular architectures not only are essential to construct smart functional materials but also provide a versatile molecular-level platform to mimic the biological transformation process. We report here the controlled self-assembly of three topologically unprecedented conjoined twin-cages, i.e.

Guest-Reaction Driven Cage to Conjoined Twin-Cage Mitosis-Like Host Transformation.

We report here a guest-reaction-induced mitosis-like host transformation from a known Pd L cage 1 to a conjoined Pd L twin-cage 2 featuring two separate cavities. The encapsulation of 1-hydroxymethyl-2-naphthol (G1), a known ortho-quinone methide (o-QMs) precursor, within the hydrophobic cavity of cage 1 is found crucial to realize the cage to twin-cage conversion. Confined G1 molecules within the nanocavity undergo self-coupling dimerization reaction to form 2,2'-dihydroxy-1,1'-dinaphthylmethane (G2) which then triggers the cage to twin-cage mitosis.

Organocatalytic Atroposelective Friedländer Quinoline Heteroannulation.

An atroposelective Friedländer heteroannulation reaction of 2-aminoaryl ketones with α-methylene carbonyl derivatives has been developed for the first time with chiral phosphoric acid as an efficient organocatalyst. The desired enantioenriched axially chiral polysubstituted 4-arylquinoline architectures were prepared with good to high yields and enantioselectivities (up to 94% yield and up to 97% ee). Furthermore, the products can be readily derivatized to afford an array of new quinoline-containing heteroatropisomers, which hold great potential in asymmetric catalysis and drug discovery.