Circularly polarized luminescence
(CPL) in two subregions of the
near-infrared (NIR) has been achieved. By leveraging the rigidity
and diminishing detrimental vibrations of the heterobimetallic binolate
complexes of erbium [(Binol)3ErNa3], species
exhibiting an exceptionally high dissymmetry factor (|g
lum |) of 0.47 at 1550 nm were obtained. These erbium
complexes are the first reported examples of CPL observed beyond 1200
nm. Analogous complexes of ytterbium and neodymium also exhibited
strong CPL (|g
lum| = 0.17, 0.05, respectively)
in a higher energy NIR window (800–1200 nm). All complexes
exhibit high quantum yields (Er: 0.58%, Yb: 17%, Nd: 9.3%) and high B
CPL values (Er: 57 M–1 cm–1, Yb: 379 M–1 cm–1, Nd: 29 M–1 cm–1). Because of
their strong CPL emission in the telecom band (1550 nm), biologically
relevant NIR emission window (800–1100 nm), and synthetic versatility,
the complexes reported here could permit further promising developments
in quantum communication technologies and biologically relevant sensors.
The synthesis of chiral C1‐symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |glum|=1.2×10−3. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL‐emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.
The synthesis of alkali metal- and halide-free mixed valent dilanthanide complexes supported by a calix[4]pyrrole ligand is described. Bond activation using both a base and one-electron reductant is showcased.
The substituent effect on the magnitude of the circularly polarized luminescence (CPL) of MentCAAC‐Cu‐X (X=F, Cl, Br, I, BH4, B3H8; CAAC=cyclic (alkyl)(amino)carbenes) complexes is experimentally investigated. This study examines seven pairs of enantiomeric complexes with small anionic substituents (halides, borohydrides, hydride). The complexes are fully characterized, including single crystal X‐ray diffraction studies, and chiroptical measurements show that small covalent anions induce a larger CPL magnitude. These results demonstrate that the magnitude of the CPL can be manipulated without making any modifications to the chiral ligand.
The synthesis of chiral C1‐symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |glum|=1.2×10−3. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL‐emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.
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