Self‐Assembly of Diacetylene‐Bridged Phenylenevinylene Oligomers in Water and Organic Solvents

Abstract

Rodlike π‐conjugated molecules in which two OPV fragments are connected through a diacetylene bond self‐assemble in aqueous and organic media. Optical spectroscopy and AFM measurements indicated that, in water, strong hydrophobic interactions between π‐cores promote aggregation into robust, uniform micellar structures. In contrast, in apolar solvents, a fibrilar morphology is obtained by coiling of columnar stacks. These stacks are formed in a nucleation‐elongation process with degrees of cooperativity of 0.006, that is influenced by the low rotation barriers around the σ‐bonds in the diacetylene linker.

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

“…These systems, bearing a phenylethynyl moiety between the central phenyl ring and the amides, show cooperative polymerizations in alkane solvents, while isodesmic polymers are formed in CHCl 3 and aqueous environments. 109,132 Compared to their smaller analogues, polymers of these extended BTAs have similar stability in MCH but show increased destabilization upon addition of CHCl 3 , presumably due to better interactions between CHCl 3 and the extended aromatic surface. 107 This effect is analogous to the trend observed in solvent-accessible surface area for protein denaturation by urea.…”

Self-Assembled Oligothiophenes for Photocatalytic Hydrogen Production and Simultaneous Organic Transformation

“…Fundamental properties, such as energy migration and charge transfer dynamics of the self-assembled organic nanostructures are contingent on their molecular packing, nature of crystallinity, and so on. Usually, various noncovalent interactions such as hydrogen bonding, π–π stacking, hydrophobic/electrostatic interactions, and van der Waals interactions, among others, are involved in the assembling process of these organic materials to form supramolecular assembled nanostructures. , Among π-conjugated molecules, the oligothiophenes and their derivatives are promising materials due to their superior properties such as long-range π-conjugation and the ability to form various highly ordered morphologies through self-assembly. ,, The self-assembled QTH nanostructures with various morphologies (such as 1D nanorods and 2D nanosheets) have been fabricated by employing coprecipitation approaches (as depicted in Figure a). The formation of various self-assembled QTH nanostructures mostly depends on the dielectric constant and polarity of solvent medium. , The QTH molecules interact with each other in a regular herringbone fashion to attain a minimal thermodynamically stable condition (minimal π–π stacking) and form various morphologies. , The growth mechanism for the self-assembled QTH nanostructures is as follows: at a very low level of water content, the QTH molecules interact in a head-to-tail position (linear fashion aggregation) and form a highly crystalline 1D nanorods-like morphology (Figure b).…”

“…32,54 Among π-conjugated molecules, the oligothiophenes and their derivatives are promising materials due to their superior properties such as long-range πconjugation and the ability to form various highly ordered morphologies through self-assembly. 23,32,55 The self-assembled QTH nanostructures with various morphologies (such as 1D nanorods and 2D nanosheets) have been fabricated by employing coprecipitation approaches (as depicted in Figure 1a). The formation of various self-assembled QTH nanostructures mostly depends on the dielectric constant and polarity of solvent medium.…”

Dinucleoside‐Based Macrocycles Displaying Unusually Large Chelate Cooperativities

“…Over the last 8 years, our research group has studied diverse nanostructured molecular systems self‐assembled through H‐bonding interactions, [14,15] including, among others, [61] (sub)phthalocyanine π‐conjugated materials, [62–67] G‐quadruplexes, [68–72] and other DNA nucleobase‐based systems [73–75] . Part of our efforts were in particular dedicated to establishing a versatile methodology to prepare macrocycles with a controlled size, shape and composition based on the H‐bonding Watson‐Crick interaction [76–81] …”