Stapled helical o-OPE foldamers as new circularly polarized luminescence emitters based on carbophilic interactions with Ag(i)-sensitivity

Abstract

Chiral stapled o-OPEs show excellent circular polarized luminescence responses (glum of 1.1 × 10–2) which can be modulated by carbophilic interactions.

Sulfoxide‐Induced Homochiral Folding of ortho‐Phenylene Ethynylenes (o‐OPEs) by Silver(I) Templating: Structure and Chiroptical Properties

“…Theoretical calculations for ligand ( S , S )‐ 3 showed a preference for the coordination of Ag I cations with the three alkynes in a helical environment, as previously observed . Such arrangement forces coordination with a OMe group, and the configuration of the helix is inverted from ( S , S , M ) in the absence of Ag I to the ( S , S , P )‐ 3 :Ag complex.…”

“…We recently showed that folded o ‐OPE‐based nanopores could be filled with silver(I) cations through carbophilic interactions with alkynes, to give a new class of metallofoldamers (Figure , acyclic achiral organic emitters) . We also synthesized helical stapled o ‐OPEs with an enantiopure 2,3‐dihydroxybutane diether moiety, which showed excellent CPL responses (Figure , cyclic chiral enantiopure organic emitters) …”

Circularly Polarized Luminescence Switching in Small Organic Molecules

“…By appropriate molecular design, the carbophilic interaction of Ag I can also act as the driving force to trigger the conformation changes and thus CPL switching for chiral fluorophores. This was well demonstrated by a Ag + ‐sensitive ortho ‐oligo(phenylene)ethylene (OPE) derivative p , p ‐ 13 (Figure ), which was reported by Cuerva and co‐workers. In compound 13 , the OPE can be fixed into a helical conformation .…”

Azabora[5]helicene Charge‐Transfer Dyes Show Efficient and Spectrally Variable Circularly Polarized Luminescence

“…With the idea to further enrich the photophysics of this fascinating platform we have built on their biaryl structure, which provides a means to arrive at dyes with helical chirality and the corresponding observation of interesting chiroptical properties, including the detection of circularly polarized luminescence (CPL) . The phenomenon is well established for supramolecular assemblies or nanostructures . However, the observation of CPL from small organic molecules (SOMs), albeit generally showing smaller dissymmetry factors ( g ), has recently created considerable interest in the dye chemistry community .…”