Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Abstract

Supramolecular polymers are a class of macromolecules stabilized by weak non-covalent interactions. These self-assembled aggregates typically undergo stimuli-induced reversible assembly and disassembly. They thus hold great promise as so-called functional materials. In this work, we present the design, synthesis, and responsive behavior of a short supramolecular oligomeric system based on two hetero-complementary subunits. These "monomers" consist of a tetrathiafulvalene-functionalized calix[4]pyrrole (TTF-C[4]P) and a glycol diester-linked bis-2,5,7-trinitrodicyanomethylenefluorene-4-carboxylate (TNDCF), respectively. We show that when mixed in organic solvents, such as CHCl , CH ClCH Cl, and methylcyclohexane, supramolecular aggregation takes place to produce short oligomers stabilized by hydrogen bonding and donor-acceptor charge-transfer (CT) interactions. The self-associated materials were characterized by H NMR and UV/Vis/NIR absorption spectroscopy, as well as by concentration- and temperature-dependent absorption spectroscopy and dynamic light scattering (DLS) analyses of both the monomeric and oligomerized species. The self-associated system produced from TTF-C[4]P and TNDCF exhibits a concentration-dependent aggregation behavior typical of supramolecular polymers. Further support for the proposed self-assembly came from theoretical calculations. The fluorescence emitting properties of TNDCF are quenched under conditions that promote the formation of supramolecular aggregates containing TTF-C[4]P and TNDCF. This quenching effect has been utilized as a probe for the detection of substrates in the form of anions (i.e., chloride) and nitroaromatic explosives (i.e., 1,3,5-trinitrobenzene). Specifically, the addition of these substrates to mixtures of TTF-C[4]P and TNDCF produced a fluorescence "turn-on" response.

Surfactant-induced chirality transfer, amplification and inversion in a cucurbit[8]uril–viologen host–guest supramolecular system

“…11–13 Chiral supramolecules 14 that consist of chiral/achiral compounds and other building blocks held together by non-covalent interactions ( e.g. , hydrogen bonding, 15,16 electrostatic interactions, 17 π–π stacking interactions, 18–20 and host–guest interactions 21 ) offer a promising strategy to build ordered chiral assembly structures and achieve versatile chiral activities at the macroscopic scale. Consequently, chirality induction, 22 transfer, 23 amplification, 24 and inversion 25–28 have been studied extensively in order to elaborate on the chiral activities in different supramolecular systems.…”

In-Situ GISAXS Study of Supramolecular Nanofibers having Ultrafast Humidity Sensitivity

“…Development of organic materials using supramolecular design stratergies 8–10 to achieve novel functionalities has been in the forefront of research interest 11–15 . Supramolecular materials are relatively new class of organic materials which are considered as promising candidates for various applications such as solar cells 16–19 , sensors 20, 21 , FETs 11, 12, 22–26 etc. Interactions in these materials benefit from the intermediate size regime (few tens of nm to µm) that lies between single molecule (few nm) and polymer thin films (~µm) 11 which enable easy fabrication.…”

Electron-Triggered Metamorphism in Palladium-Driven Self-Assembled Architectures

“…[15][16][17][18][19][20][21][22][23] It includes the ability to undergo assembly/disassembly processes under specific conditions, to adapt to their environment with changes in shape and size or to spontaneously repair structural damages (self-healing). [24][25][26][27][28][29][30][31][32] One strategy that has been used to expand the application scope of self-assembled systems relies on the use of metal ions as building elements. The so-called "metal-driven self-assembly approach" has indeed been explored since the early nineties with most transition metals to give access to a wide range of metal-ligand assemblies with interesting properties for applications in various research fields ranging from catalysis to material science.…”