Chiral Macrocyclic AIEgens from BINOL and Tetraphenylethene via Tailoring Chirality of Luminescent Molecular Propellers

Abstract

Herein, a pair of chiral macrocyclic luminogens derived from chiral 1,1-bi(2-naphthol) (BINOL) and tetraphenylethenes (TPEs) have been prepared with high yield via intramolecular McMurry coupling, in which the preferential helicity of propeller-shaped TPE units can be tuned via choosing proper chiral BINOL tethers. The preferential chiral geometry of the macrocyclic luminogen was unambiguously confirmed by X-ray crystal crystallography and theoretical calculation, whereas the variable-temperature NMR spectra and chiral HPLC analysis further verified the intramolecular motions. These two chiral macrocyclic luminogens both exhibit obvious aggregation-induced emission behavior and mechanochromic luminescence properties. Furthermore, aggregation attenuated CD signals and circularly polarized luminescence were observed for these two chiral macrocylic luminogens in THF-water mixture and PMMA matrix. These results had paved a new approach toward constructing chiral aggregation-induced emission luminogens (AIEgens) and their structural engineering.

Full-color-tunable Chiral Aggregation-induced Emission Fluorophores with Tailored Propeller Chirality and their Circularly Polarized Luminescence

“…Therefore, the precise molecular geometry and inherent chirality of these chiral AIEgens were defined based on the crystal structures of previously reported building blocks RBTPE and SBTPE . [42] As previously reported, the introduction of R-BINOL moiety would induce theP -helicity for TPE fluorophores within the cyclic skeleton, whereas the S-BINOL moiety would render the TPE core M -helicity. And thus, the TPE moiety in RBTPE-Br , RBTPE-CHO ,RBTPE-CN and RBTPE-2CN would correspondingly adaptP -helicity, whereas the TPE unit in their counterparts displayedM -helicity.…”

“…[39][40][41] Recently, the commercial available BINOL (1,1'-binaphth-2,2'-diol) moiety with defined axis chirality has been leveraged to tether the helicity of TPE cores via chirality transfer in the macrocyclic skeleton. [42][43][44] Based on the intramolecular McMurry coupling, [45] our group have readily synthesized a pair of chiral macrocyclic TPE derivatives (denoted asRBTPE and SBTPE) with high yield and stereo-selectivity,. [42] The helicity of propeller-like TPE moiety within the macrocyclic backbones is feasibly pre-determined by the chiral BINOL moiety, and unambiguously confirmed via single crystal analysis.…”

“…[42][43][44] Based on the intramolecular McMurry coupling, [45] our group have readily synthesized a pair of chiral macrocyclic TPE derivatives (denoted asRBTPE and SBTPE) with high yield and stereo-selectivity,. [42] The helicity of propeller-like TPE moiety within the macrocyclic backbones is feasibly pre-determined by the chiral BINOL moiety, and unambiguously confirmed via single crystal analysis.…”

From luminescent π-conjugated macrocycles to bridged multi-cyclic π-conjugated polymers: cyclic topology, aggregation-induced emission, and explosive sensing

“…Firstly, the half-ring precursors 1 and 2 with two benzophenone terminals were readily synthesized via Suzuki coupling (Schemes S1 and S2†). Then the “semicircle” precursors were converted to conjugated macrocycles [6]CTPE and [10]CTPE via intermolecular McMurry coupling, 24 whereas the conjugated scaffold of macrocycles featured six or ten phenyl rings in the cyclic backbone, respectively (Scheme 1). For the cyclic monomers, two reactive chloride groups had been retained at the apex of the rigid ring.…”

One‐Pot Synthesis of Axially and Centrally Chiral A‐type Nanogrids

“…[ 21‐22 ] Of these, biaryl axially chiral molecules, particularly 2,2’‐disubstituted derivatives of 1,1’‐binaphthyl, are a versatile class of compounds that have found applications in many areas of chemistry and material. [ 23‐25 ] The robust configurational stability of binaphthyl derivatives in a broad range of conditions, [ 26 ] combined with their tunable chiral dihedral angle, makes them an ideal platform for transferring stereoinformation and exhibiting excellent optical properties. [ 27 ] Here, we propose a fascinating class of A‐type nanogrids (AGs), which consist of difluorenyl biaromatic derivatives (green and blue, A2 synthons which represent two reaction sites) and thiophene derivatives (red, B2 synthons which represent two reaction sites, Figure 1).…”