Finely Resolved Threshold for the Sharp M₁₂L₂₄/M₂₄L₄₈ Structural Switch in Multi‐Component M_nL_2n Polyhedral Assemblies: X‐ray, MS, NMR, and Ultracentrifugation Analyses

Abstract

In the self-assembly of M(n)L(2n) polyhedra, the bend angle (θ) of the divalent ligand components determines the final structure. The threshold for the sharp structural switch between M12L24 and M24L48 was finely resolved to within just 4° by demonstrating the exclusive formation of M12L24 cuboctahedra or M24L48 rhombicuboctahedra from two similar ligands with θ values of 130° and 134°. This sharp structural switch was fully confirmed by X-ray crystallography, mass spectrometry, NMR spectroscopy, and ultracentrifugation analyses.

A Pt(II)‐based Hexagonal Ionic Supramolecular Coordination Complex and its DNA Interactions.

“…In this proton‐decoupled spectrum, the two signals at δ 22.70 ppm and δ 8.48 ppm are satellite peaks obtained due to spin‐spin coupling of two equivalent 31 P nuclei that are directly bonded to the spin‐active 195 Pt (I = , 33.8 %) center. The magnitude of coupling constant ( 1 J PPt =1151 Hz) was similar to that observed for previously reported SCCs bearing Pt‐N(pyridyl) bonds . Appearance of a single peak in the phosphorus NMR spectrum strongly suggests presence of a single and highly symmetrical species .…”

“…It was anticipated that use of 4,6‐diiodopyrimidine instead of the corresponding dichloro derivative would result in a better yield of the target molecule ( 1 ) via Sonogashira cross‐coupling with 3‐ethynylpyridine. Thus 4,6‐dichloropyrimidine was first converted into 4,6‐diiodopyrimidine by reacting it with hydroiodic acid for 2h at room temperature (yield = 85 %) . 3‐ethynylpyridine was easily obtained from 3‐iodopyridine .…”

Self-Assembly of M 30 L 60 Icosidodecahedron

“…33 In theory, the ideal bend angle q can be calculated mathematically for any target polyhedral, for example, q = $90 for M 6 L 4 , q = $120 for M 12 L 24 , and q = $135 for M 24 L 48 . For n % 24, 29,30,34 this guiding principle works well. However, we found that the self-assembly of thiophenecored ligand (1, q = 149 ), even with a q value close to the ideal bend angle for M 30 L 60 (q = 150 ), still formed M 24 L 48 rather than M 30 L 60 .…”

Broadening the catalytic region from the cavity to windows by M6L12 nanospheres in cyclizations

“…A powerful strategy to produce pyridine-coordinated palladium M n L 2 n ( n = 6, 12, 24) cages was pioneered by Fujita. 7 The combination of the ditopic bispyridine building blocks and palladium complexes typically afforded self-assembled structures such as M 6 L 12 , M 12 L 24 and M 24 L 48 , 8,9 depending on the bend angle of the bispyridine building blocks. The M 12 L 24 nanospheres are amongst the most widely studied, as they can be functionalized with facile endohedral or exohedral binding groups, thereby generating a confined microenvironment suited for potential applications.…”