Covalently Trapped Triarylamine‐Based Supramolecular Polymers

Abstract

C 3 -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups,u ndergo supramolecular polymerization and further gelation by p-p stacking and hydrogen bondingoftheir TATA cores.B yusing subsequentr ing-opening metathesisp olymerization, these physical gels are permanently crosslinked into chemical gels. Detailedc omparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by opticals pectroscopies, electronic spectroscop-ies, atomicf orce microscopy,e lectronic paramagnetic resonance spectroscopy,X -ray scattering, electronic transport measurements, and rheology.T he resultsp resented here clearlye vidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalentc apturew hereas the mechanical properties of the gels are concomitantly improved, with an increaseo f their storagemodulusb yt wo orders of magnitude.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Triarylamine Enriched Organostannoxane Drums: Synthesis, Optoelectrochemical Properties, Association Studies, and Gelation Behavior

“…In general, organogels are appealing in multiple research fields due to their extremely wide range of applications in optoelectronics and photovoltaics, − pharmaceutics and biochemistry, − sensing, , and different branches of organic chemistry. − Moreover, organogels with luminescent properties are raising further interest within the fields of chemical sensing and electronics . Organogels could be presented with a huge variety of molecular structures; however, just a few of these studies have focused on triarylamine (TAA)-substituted compounds. ,− TAAs are known for their outstanding electronic properties, such as their satisfactory hole mobility, and are therefore highly employed in photovoltaics. − TAAs tend to gelificate in aromatic solvents, mostly due to π–π interactions. The modification of the TAA substituents can modulate the properties of the final compound. , For example, some TAA gels showed the ability to absorb in the near-infrared (NIR) region and might therefore be useful in solar control devices …”

“…Organogels could be presented with a huge variety of molecular structures; however, just a few of these studies have focused on triarylamine (TAA)-substituted compounds. ,− TAAs are known for their outstanding electronic properties, such as their satisfactory hole mobility, and are therefore highly employed in photovoltaics. − TAAs tend to gelificate in aromatic solvents, mostly due to π–π interactions. The modification of the TAA substituents can modulate the properties of the final compound. , For example, some TAA gels showed the ability to absorb in the near-infrared (NIR) region and might therefore be useful in solar control devices …”

“…The modification of the TAA substituents can modulate the properties of the final compound. 26,34 For example, some TAA gels showed the ability to absorb in the near-infrared (NIR) region and might therefore be useful in solar control devices. 25 Herein, the synthesis of three new molecules with a stannoxane drum-like core decorated with six triarylaminecontaining wedges (compounds 1, 2, and 3, Figure 2) is reported.…”

“…In line with the reported literature, the formation of the gel was not observed in polar solvents. 26,34 The formation of organogels is indicative of the achievement of the long-range organization of the molecules of 1. 19,41−44 This organization is induced by the biased noncovalent interactions of the molecules that give rise to a microstructured network that spans the entire sample, thus immobilizing the solvent.…”

Interplay Between Hydrogen Bonding and Electron Transfer in Mixed Valence Assemblies of Triarylamine Trisamides

“…Giuseppone and co‐workers disclosed the particularly impressive conductive properties of fibers built on C 3 ‐symmetrical triarylamine trisamide (TATA) monomers, after their irradiation in chlorinated solvents or in presence of suitable oxidants [34] . Supramolecular delocalized polarons [43] that result from the fast through‐space electron transfer between the connected units make TATA fibers an interesting platform for the design of processable optoelectronic materials [40,44–46] . As TA compounds do not exhibit such behavior, hydrogen bonding interactions are assumed to be key for the generation of electroactive supramolecular TA‐based polymers.…”