Homologous and Heterologous Chiral Supramolecular Polymerization from Exclusively Achiral Building Blocks

Abstract

Among the enticing issues of chiral origins are: how chirality is born from the initial achiral units and the mechanisms for the transfer of chiral information. In this work, by combining a physical vortex and chiral seeds, a general process is revealed to generate chiral supramolecular polymers from achiral C3‐symmetric molecules. The symmetry‐broken assemblies from the achiral molecules could work as chiral seeds to initiate the polymerization of either homologous or heterologous achiral monomers. Concomitantly, the fragmentation of the polymer caused by the vortex during the nucleation‐elongation stages is shown to enlarge the domains of the chiral nuclei and then guide the polymer to grow into the predominant helicity with a high reactivity ratio. Moreover, the chiral structural information can be stored in different forms of assemblies. These new polymerization modes will provide guidance for the preparation of chiral materials.

Chiral hybrid manganese(ii) halide clusters with circularly polarized luminescence for X-ray imaging

“…2a and c, between 300 nm and 550 nm, R/S-1 and R/S-2 exhibit three dominant excitation peaks. The PLE spectrum of R/S-1 includes several bands at 360, 372, 424, 448, and 525 nm, which correspond to electronic transitions from the 6 A 1 ground state of Mn 2+ ions to 4 E g (D), 4 T 2g (D), [ 4 A 1g (G), 4 E g ], 4 T 2g (G), and 4 T 1g (G), respectively. The peak emission is located around 638 nm, with a full width at half-maximum (FWHM) of 75 nm, which occurs due to the 4 T 1 (G) to 6 A 1 radiative transition of octahedrally coordinated Mn 2+ in the inorganic framework [Mn 3 Cl 12 ] 6À .…”

“…In Fig. 2b, the excitation bands of R/S-2 are located at 360, 372, 424, 445, and 526 nm, which are attributed to electronic transitions of Mn 2+ from the ground state to 4 E g (D), 4 T 2g (D), [ 4 A 1g (G), 4 E g ], 4 T 2g (G), and 4 T 1g (G), respectively. There are emission peaks of 650 nm as well as the FWHM of 75 nm, and these correspond to the T 1 (G)-6 A 1 radiative transition of Mn 2+ in the inorganic framework [Mn 3 Cl 12 ] 6À units.…”

“…Materials with circularly polarized luminescence (CPL) have attracted widespread attention due to their wide potential applications for 3D displays, optical data storage, photoelectric devices, asymmetric synthesis, and so on. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] In general, the degree of circular polarization is defined by the strength of left and right circularly polarized light (I L and I R ). 20 In order to effectively evaluate the intrinsic properties of CPL materials, the luminescence dissymmetry factor (g lum ) is defined as the difference between the strength of I L and I R divided by their average total luminescence strength, namely g lum = 2 Â (I L À I R )/ (I L + I R ).…”

Arene‐Perfluoroarene Force Driven Sublimation‐Removable Chiral Coassemblies

“…Noncovalent interactions including hydrogen bonding, halogen bonding, electrostatic attraction, van der Waals, π–π stacking, metal‐ligand coordination charge‐transfer and others were employed to integrate components to afford supramolecular complexes, whereby the asymmetrical packing and chiroptical features could be rationally manipulated [28–40] . Achiral entities intercalated into chiral building units to induce the emergence and inversion of supramolecular chirality [41, 42] . Organic and inorganic luminescent species coassemble with chiral matrices enable the colorful circularly polarized luminescence (CPL) at full wavelength ranges [43] .…”

“…[28][29][30][31][32][33][34][35][36][37][38][39][40] Achiral entities intercalated into chiral building units to induce the emergence and inversion of supramolecular chirality. [41,42] Organic and inorganic luminescent species coassemble with chiral matrices enable the colorful circularly polarized luminescence (CPL) at full wavelength ranges. [43] Coassembly could also accelerate the intersystem crossing to enable triplet emission, that the circularly polarized phosphorescence and even long afterglow have been realized.…”