Radical-Induced Hierarchical Self-Assembly Involving Supramolecular Coordination Complexes in Both Solution and Solid States

Abstract

To explore a new supramolecular interaction as the main driving force to induce hierarchical self-assembly (HSA) is of great importance in supramolecular chemistry. Herein, we present a radical-induced HSA process through the construction of well-defined rhomboidal metallacycles containing triphenylamine (TPA) moieties. The light-induced radical generation of the TPA-based metallacycle has been demonstrated, which was found to subsequently drive hierarchical selfassembly of metallacycles in both solution and solid states. The morphologies of nanovesicle structures and nanospheres resulting from hierarchical self-assembly have been well-illustrated by using TEM and high-angle annular dark-field STEM (HAADF-STEM) micrographs. The mechanism of HSA is supposed to be associated with the TPA radical interaction and metallacycle stacking interaction, which has been supported by the coarse-grained molecular dynamics simulations. This study provides important information to understand the fundamental TPA radical interaction, which thus injects new energy into the hierarchical self-assembly of supramolecular coordination complexes (SCCs). More interestingly, the stability of TPA radical cations was significantly increased in these metallacycles during the hierarchical self-assembly process, thereby opening a new way to develop stable organic radical cations in the future.

Higher-order interfiber interactions in the self-assembly of benzene-1,3,5-tricarboxamide-based peptides in water

“…[2][3][4][5] Mimicking such interactions in aqueous media with synthetic supramolecular systems remains a formidable task due to the complex and frequently counterintuitive self-assembly mechanisms. 6 In the last few decades multiple supramolecular systems with hierarchical self-assembly were reported, including coordination complexes, [7][8][9] porphyrins, 10 different peptides [11][12][13][14] including di-and tri-peptides with different motifs; 15,16 as well as synthetic 17,18 and natural 19,20 polymers. Multi-level control over self-assembly has paved the way for the development of novel advanced materials in medicine and industry; [21][22][23] however, their complexity remains distant from that observed in nature.…”

Effective Design Strategy of Small Bipolar Molecules through Fused Conjugation toward 2.5 V Based Redox Flow Batteries

“…The electrochemical EPR spectra shown in Figure 5 a indicated radical signals at both the oxidized and reduced states of QPT-OMe, and the spectra match well with simulated spectra. 66 , 67 At the oxidized state, the spectrum exhibited three peaks with strong hyperfine coupling ( a ≈ 0.65 mT). This is attributed to the localized radical electron that is distributed mainly around the N and S atoms in the phenothiazine moiety and extends to the entire conjugated structure, as revealed by the spin density distribution shown in Figure 5 b.…”

Guest-Induced Enantioselective Self-Assembly of a Pd6 Homochiral Octahedral Cage with a C3-Symmetric Pyridyl Donor

“…Self-assembly of discrete molecular architectures of diverse shapes/functionality has become one of the fascinating research areas in supramolecular chemistry. − In the past two decades, chemists have enriched the “molecular library” by reporting numerous architectures of defined shapes, sizes, and functionality. − Although metal–ligand coordination driven self-assembly of achiral building blocks mostly yields symmetric architectures, − it has become an exciting trend to derive asymmetric architectures from symmetric building units in recent time. − Square-planar metal ions such as Pd­(II) and Pt­(II) are not preferred choices for this purpose, as they generally possess a symmetric planar configuration around the metal-center . In spite of this general behavior, square-planar metal ions like Pd­(II) can be tricked to form asymmetric/chiral discrete architectures with appropriate ligands .…”