Spatiotemporal dynamics of supramolecular polymers by in situ quantitative catalyst-free hydroamination

Abstract

A supramolecular polymer based on ethynyl core-substituted naphthalenediimides reacted with various amines quantitatively without a catalyst, exhibiting unconventional reaction kinetics and products.

Functionalization of Electrode Surfaces with Reactive Supramolecular Oligomers Enables the Control of Monolayer Properties to Restore Electrochemical Reversibility

“…In contrast to similar rylene-based building blocks that form supramolecular polymer following a nucleation-elongation mechanism in an aprotic solvent, the isodesmic growth mechanism elucidated for the b-NDI-(CCH) 2 building block in water traces its origin from the inability of the NDI units to form dormant monomers. Indeed, the interaction of the amide-derived side chains with water molecules hampers the formation of intramolecular hydrogen bonds. , …”

“…Indeed, the interaction of the amide-derived side chains with water molecules hampers the formation of intramolecular hydrogen bonds. 51,52 To further confirm the existence of oligomeric species formed upon aggregation of the NDI building block in water, diffusion-ordered NMR spectroscopy (DOSY) was performed in differing ratios of deuterated acetonitrile and water at a concentration of [NDI] = 1 mM. Based on the acquired DOSY spectra shown in Figure S9, the diffusion coefficients are estimated to be 2.30 × 10 −10 m 2 /s in a 65:35 (v/v) CD 3 CN/ D 2 O solution and 9.10 × 10 −11 m 2 /s in 100% D 2 O.…”

Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust light-harvesting nanoscale objects

“…1A attaches freestanding tether units to non-covalent assemblies. [21][22][23] This method opens new avenues to modulate the (opto)electronic properties of π-SPs by exploiting the molecular tethers as synthetic handles. For example, we have shown that the structure of the tethers can be used to precisely control the ground-and excited-state electronic properties of stapled assemblies.…”

One-step synthesis of perylenediimides exhibiting near-infrared absorption and emission by amino–yne click reaction

“…In an effort to develop new rylene diimides with electron-rich substituents that can be obtained by a simple yet efficient synthetic route, our group has found a catalyst-free amino–yne click reaction of ethynyl-appended rylene diimides. 9 The resulting product is an electron donor (amino group) and acceptor (rylene diimide) conjugate bridged by an enamine structure, which exhibits intense CT absorption in the vis-NIR region. This feature is notable because other conventional click reactions do not bridge the electron donor and acceptor by π-conjugated structure.…”