Enantiomeric MOF Crystals Using Helical Channels as Palettes with Bright White Circularly Polarized Luminescence

Abstract

The host–guest chemistry of metal–organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology‐like H‐bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (glum) of the host l/d‐CMOF (±1.50 × 10−3) to a maximum of ±0.0115 for the composite l/d‐CMOF⊃fluorophores. l/d‐CMOF⊃fluorophores in pairs generate bright color‐tunable CPL and almost ideal white CPL (0.33, 0.32) with a record‐high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light‐emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.

Generating circularly polarized luminescence from clusterization‐triggered emission using solid phase molecular self-assembly

“…The efficiency of energy transfer E FRET is defined with respect to r and R o , the characteristic Förster distance 76 for the donor and acceptor pair by where R 0 is a characteristic distance for the donor–acceptor combination at which E FRET takes the value 0.5. Experimentally, FRET can be detected in several ways 77 – 81 . Energy transfer causes quenching of donor fluorescence and sensitized fluorescence of the acceptor.…”

Frontiers in circularly polarized luminescence: molecular design, self-assembly, nanomaterials, and applications

“…CPL-active MOFs are promising functional materials in light of their potential applications in enantiomeric separation, chiral sensors, and asymmetric catalysis [207][208][209][210][211]. In the past few years, two kinds of CPL-active MOFs have been fabricated.…”

“…(d) Scheme illustration of the coordination assembly to form chiral MOF 63 [208]. (e) Graphical representation of the formation and FRET-amplified CPLs of dye-doped chiral MOF 64 [209] (color online).…”

Chiral Induction in Buckminsterfullerene Using a Metal–Organic Framework

“…Thus, the use of chiral MOFs as host matrices should be a useful method applicable to a variety of chirality applications. [21] We believe that our methodology has paved a new avenue for future applications of the dynamic chiral induction and uncovered the elusive mechanism of spontaneous symmetric breaking.…”