Chiroptical regulation of macrocyclic arenes with flipping-induced inversion of planar chirality

Abstract

Studies on various macrocyclic arenes have received increasing attention due to their straightforward syntheses, convenient derivatization, and unique complexation properties.

Hierarchical chirality transfer of perylene diimide-tethered pillar[5]arenes for configuration and type differentiation of amino acid derivatives

“…Chirality sensing with macrocyclic arenes, such as pillar[ n ]arenes (P[ n ]), is particularly attractive because of their versatile binding ability and spectral response generated by the aromatic subunits. 5,25 P[ n ] may adopt either R p or S p conformers in the solution, which could rapidly interconvert in the solution via the flipping-induced inversion of planar chirality (FIIPC). 14 We and others have recently demonstrated that the complexation of a chiral guest will shift the R p or S p conformers of P[5]s and lead to strong ECCD signals, which is promising in application of chirality sensing.…”

“…Supramolecular chirality has been attracting wide attention and has given rise to many intriguing research topics, such as chirality induction, transfer, sensing, memory and amplification. 1–8 Supramolecular chirality sensing is promising for detecting absolute configuration and optical purity based on spectroscopic methods, including UV/Vis spectra, fluorescence, NMR and circular dichroism (CD) spectroscopies. 9–13 Compared to conventional chromatographic techniques, supramolecular chirality sensing offers the benefit of rapid and inexpensive high-throughput screening.…”

Chirality Induction and Memory of Pillar[4]arene[1]quinone Derivatives in Visible-Light Range

“…16 P [5]s possess R p (R p , R p , R p , R p , R p ) and S p (S p , S p , S p , S p , S p ) planar chiral conformers which typically interconvert through the flipping-induced inversion of planar chirality (FIIPC). 17 The complexation of a chiral guest with P [5] could shift the racemic equilibrium of the R p and S p conformers, thereby inducing significant circular dichroism (CD) responses. Moreover, the induced enantiomeric excess can be memorized by strategically controlling the racemization kinetics of the conformers through adjustments to the steric hindrance of side chain groups.…”

“…Among these, pillar[5]­arene (P[5]) and its derivatives stand out for their efficient sensing and recognition of diverse chiral guests . P[5]­s possess R p ( R p , R p , R p , R p , R p ) and S p ( S p , S p , S p , S p , S p ) planar chiral conformers which typically interconvert through the flipping-induced inversion of planar chirality (FIIPC) . The complexation of a chiral guest with P[5] could shift the racemic equilibrium of the R p and S p conformers, thereby inducing significant circular dichroism (CD) responses.…”

Fluorescence-enhanced supra-amphiphiles based on pillar[5]arene: construction, controllable self-assembly and application in cell imaging

“…16 Composed of five hydroquinone units connected by methylene at the para-position, pillar [5]arenes have pillar-like structures [17][18][19][20][21] The symmetrical structures and easy functionalization endow pillar [5]arene with good properties in host-guest chemistry. [22][23][24][25][26][27] Owing to the significant efforts of scientists, numerous stimuli-responsive host-guest recognition motifs of pillar [5]arenes have been constructed and further utilized in the production of various materials, including pillar [5]arene-based supramolecular polymers and supramolecular amphiphiles. [28][29][30][31][32] In stark contrast, only a limited number of attempts have been made to investigate fluorescence properties of pillar [5]arene-based host-guest systems.…”