Autoresolution of Segregated and Mixed p‐n Stacks by Stereoselective Supramolecular Polymerization in Solution

Abstract

A "chirality driven self-sorting" strategy is introduced for the controlled supramolecular organization of donor (D) and acceptor (A) molecules in multicomponent assemblies. The trans-1,2-bis(amido)cyclohexane (trans-BAC) has been identified as a supramolecular motif with strong homochiral recognition to direct this chirality controlled assembly process of enantiomers in solution. Stereoselective supramolecular polymerization of trans-BAC appended naphthalene diimide monomers (NDIs) has been probed in detail by spectroscopic and mechanistic investigations. This chirality-driven self-sorting design of enantiomeric components also offers to realize mixed and segregated D-A stacks by supramolecular co-assembly of the NDI acceptors with trans-BAC appended dialkoxynaphthalene (DAN) donor monomers. Such an unprecedented chirality control on D-A organization paves the way for the creation of supramolecular p-n nanostructures with controlled molecular-level organization.

Enantioselective Light Harvesting with Perylenediimide Guests on Self‐Assembled Chiral Naphthalenediimide Nanofibers

“…[8b] Thea bsorption spectrum of 1 shows two distinct absorption bands.The absorption band below 400 nm corresponds to the electronic transition along the long axis of the NDI core. [21][22][23][24][25] These results indicate that the electronic coupling between the NDI p-orbitals in the selfassembled system is limited owing to the interruption of the strong p-p stacking interactions between NDI cores by the ethoxy groups. [27] Thes tructure of the latter band is almost retained even after self-assembly whereas broadening was observed for the former band.…”

“…Theb uilding blocks of supramolecular assemblies play adecisive role in dictating their functional properties.The use of PDIs [7a] in this regard has been well established in the literature;more recently,ithasbeen reported that NDIs also fall into this category. [20][21][22][23][24][25][26] Fore xample,G eorge and coworkers reported that a trans-1,2-diamide cyclohexane derivative bearing two NDI units (2;S cheme 1) underwent autoresolution during enantioselective self-assembly,demonstrating its chiral recognition capability. [25b] However, 2 is less emissive,w hich limits studies based on energy transfer and CPL.…”

Controlling supramolecular polymerization through multicomponent self‐assembly

“…339 George and coworkers reported the co-assembly of pconjugated amphiphilic building blocks. [340][341][342][343][344][345][346] Using the electron-rich coronene/electron-deficient methyl viologen pair, 340 or oligo(phenylenevinylene) (OPV1)/perylene diimide (PDI1) pair, 341 the formation of supramolecular alternating electron-donor/acceptor arrays were obtained. Both comonomer pairs, the cationic viologen and the anionic coronene tetracarboxylate, and the cationic ammoniumfunctionalized PDI1 and the anionic OPV dicarboxylate OPV1 form charge transfer complexes and coassemble into 1-D nanofibers in water with an alternating comonomer arrangement, which from hydrogels at millimolar concentrations of the building blocks (Fig.…”

Self‐Sorting in Supramolecular Assembly of π‐Systems

“…In the recent past, examples showed that chirality might also lead to the self‐sorted assembly. George and co‐workers studied chirality driven self‐sorting of donor‐acceptor chromophores (Figure ) using trans‐1,2‐bis(amido) cyclohexane (BAC) supramolecular motif . They designed RR ‐NDI, SS ‐NDI, RR ‐DAN and SS ‐DAN building blocks (29–32) by linking the DAN/ NDI chromophores to the trans‐BAC motif.…”