Chirality-Controlled Supramolecular Donor–Acceptor Copolymerization with Distinct Energy Transfer Efficiency

Abstract

Chirality delivers substantial value to the field of supramolecular polymers, not only serving as a probe to monitor the dynamic assembly process but providing access to chiroptical materials. The current study demonstrates that, for supramolecular donor–acceptor copolymers, their comonomer organization modes can be greatly influenced by stereocommunication at the molecular level. The enantiopure N-[(1R or 1S)-phenylethyl]­benzamides are incorporated into two structurally similar comonomers, locating between the π-aromatic diethynylacene core and the alkyl chain peripheries. Parallel arrangement of the stereogenic methyl units brings steric hindrance between the homochiral comonomers, which is relieved for the heterochiral comonomers due to the adoption of staggered arrangement. It consequently steers randomly mixed organization for the homochiral supramolecular copolymers within the nanofibers. In comparison, the heterochiral counterparts form nanoparticles in an alternate donor–acceptor organization manner. The variation of comonomer arrangement modes gives rise to distinct energy transfer efficiency at the supramolecular level. Overall, the elaborate manipulation of stereogenic centers in the comonomer structures exerts significant impacts on the characteristics of supramolecular copolymers, which could be useful for chiral sensing, recognition, and optoelectronic applications.

Supramolecular Block Copolymers from Tricarboxamides. Biasing Co‐assembly by the Incorporation of Pyridine Rings

“…The analysis of the bond fraction corroborates the microstructure of poly‐1‐co‐4 . Thus, the similar bond fraction of both homopolymers, ≈0.20 at 20 °C, and the heteropolymer, ≈0.30 at 20 °C, is diagnostic of random homo‐ and heterointeractions of the two monomeric species within the supramolecular copolymeric chain (Figures S11b and 1d) [15] …”

Large Optical Asymmetry in Silver Nanoparticle Assemblies Enabled by CH−π Interaction-Mediated Chirality Transfer

“…Nature uses the molecular asymmetry to create biomolecular assemblies through fine-tuning of multiple noncovalent interactions, which is essential to the operation of molecular machines or the functionality macroscopically. − Inspired by biomolecular systems, chemists have created a variety of chiral molecular/supramolecular systems aiming to reveal principles about how to design and assemble functional molecular systems with increasing complexity. − Despite the good understanding of the chirality at the molecular/supramolecular level, the study of chirality at the nanoscale, such as chiral inorganic nanostructures, is still in its infancy and, an important challenge remainshow the chirality at the molecular level can be translated to asymmetry at the nanoscale. − One practical approach to connect the molecular chirality to inorganic nanoparticles (NPs) is to functionalize the NPs with chiral organic ligands to render individual NP chiral atomically, which, however, is limited by the specific covalent/coordinating bonding between NPs and chiral ligands. − These limitations can be overcome by chiral templating where the asymmetric features of the templates can be well imprinted into the NP assemblies . But such chiral templating highly depends on the intermolecular interaction between the chiral templates and NPs, which greatly determines the induced asymmetry factor of the chiral NP assemblies. , Hence, it remains a challenging task to rationalize the affinity between the chiral templates and the NPs.…”

Probing Achiral Benzene‐1,3,5‐tricarboxamide Monomers as Inducers of Homochirality in Supramolecular Helical Catalysts**

“…[16,17] In most of these systems, chiral and achiral monomers have roughly similar (co-)equilibrium constants leading to copolymers with a presumably random distribution of the monomers. [18] However, recent studies [5] demonstrated that subtle differences in these constants for cooperative supramolecular polymer assembly are key to manipulate the length and degree of association, [19][20][21][22][23][24] as well as the composition and monomer sequence [25][26][27][28] in the copolymers, with deep consequences on their rheological [20] and catalytic properties. [24] Recording the variation of the copolymer structural parameters under various conditions, e. g. temperature and concentration, fitted with thermodynamic mass-balance models, may allow to determine the role of the "sergeant" a posteriori, [23] but no design of the "sergeant" can be made a priori.…”