Interconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules

Abstract

Research into stimuli-responsive controlled self-assembly and reversible transformation of molecular architectures has received much attention recently, because it is important to understand and reproduce this natural self-assembly behavior. Here, we report two coordination nanocapsules with variable cavities: a contracted octahedral V24 capsule and an expanded ball-shaped V24 capsule, both of which are constructed from the same number of subcomponents. The assemblies of these two V24 capsules are solvent-controlled, and capable of reversible conversion between contracted and expanded forms via control of the geometries of the metal centers by association and dissociation with axial water molecules. Following such structural interconversions, the magnetic properties are significantly changed. This work not only provides a strategy for the design and preparation of coordination nanocapsules with adaptable cavities, but also a unique example with which to understand the transformation process and their structure-property relationships.

Equi–size nesting of Platonic and Archimedean metal–organic polyhedra into a twin capsid

“…Whereas for 1a, the χ M T value of 4.2 cm 3 K mol -1 is much lower than the excepted value (9.0 cm 3 K mol -1 ). The magnetism is contributed by the tetravalent V IV ions rooting in outer-shell uninucleate V IV and {V 5 O 9 Cl} clusters, wherein the {V 5 O 9 Cl} includes four uncoupled V IV (S = 1/2, g = 2.00) 19,40,41 and a central diamagnetic V V ion. As the temperature decreased from 300 to 100 K, the changes of χ M T vs. T data for 1 and 1a trend to be similar, namely the χ M T value of both 1 and 1a slightly decrease.…”

“…The design synthesis of double-shell architectures is still an elusive target for researchers. Unlike single-wall molecular aggregates [18][19][20][21] , the intrinsic structural particularity of doubleshell MOPs sets a higher requirement for building components, especially for organic ligands in that how to reinforce structural subdivision is a key factor to be considered in the process of selfassembly. Because of this, with the exception of a few sporadic reports on metal-organic frameworks (MOFs) containing doubleshell subunits so far [22][23][24][25][26] , double-shell macromolecular cages are much more rarely observed in the literature, with Pd-involved self-assembly being the commonest.…”

Coordination‐Assembled Molecular Cages with Metal Cluster Nodes

“…Yuan group have reported two similar cages, V 24 (C‐Propylpyrogallol[4]arene) 6 ( MCCC‐69 ), which consists of a contracted octahedral capsule ( 69‐oct ) and an expanded ball‐shaped capsule ( 69‐ball ) from the same number of subcomponents including 6 pyrogallol[4]arene units and 8 trinuclear V 3 clusters (Figure 19). [41] 69‐oct‐α was obtained by combining PgC 3 with VOSO 4 ⋅ 5H 2 O in CH 3 CN/H 2 O solution at 80 °C for three days, with the formula [V 24 O 24 (H 2 O) 24 (C 40 H 40 O 12 ) 6 ] ⋅ (solvent) x . According to the single crystal structure, the V ions are six‐coordinated in octahedral geometries and coordinated with four phenoxyl oxygen atoms from two different PgC 3 ligands, one interior water molecule, and one exterior oxygen atom.…”

Efficient ethylene purification by a robust ethane-trapping porous organic cage

“…They possess electron-rich π cavities and eight upper-rim phenolic groups, and have been determined to be effective hosts for inclusion of a variety of guests range from small gases to large organic molecules [44][45][46][47][48] . Notably, their upper rims can be easily functionalized, and this makes them good molecular building blocks for construction of self-assembled cages as well as porous polymers [49][50][51][52][53][54][55] . Very recently, by using pre-designed concave-shaped tetraformylresorcin [4] 56 .…”