Chiral Molecular Ruby [Cr(dqp)(2)](3+) with Long-Lived Circularly Polarized Luminescence

Jimenez, Juan-Ramon; Doistau, Benjamin; Cruz, Carlos M.; Besnard, Caine; Cuerva, Juan M.; Campana, Araceli G.; Piguet, Claude

VL / 141 - BP / 13244 - EP / 13252
The chiral resolution of a kinetically inert molecular ruby [Cr(dqp)(2)](3+) (1, dqp = 2,6-di(quinolin-8-yl)pyridine) displaying strong dual light emission at room temperature has been achieved. The wrapped arrangement of the six-membered dqp chelating ligands around the Cr(III) provided nonplanar helical conformations leading to the diastereoselective assembly of chiral bistridentate monometallic Cr(III)-helix. The PP-(+)-[Cr(dqp)(2)](3+) and MM-(-)-[Cr(dqp)(2)](3+) enantiomers could be separated and isolated by using cation-exchange chromatography and subsequent salt-metathesis with KPF6. X-ray crystallographic analysis based on Flack parameters assigned the absolute configurations of the two enantiomers. Circularly polarized luminescence (CPL) spectra showed two polarized emission bands within the NIR region corresponding to the characteristic metal-centered spin-flip Cr(E-2 -> (4)A(2)) and Cr(T-2(1) -> (4)A(2)) transitions with exceptionally high dissymmetry factors, vertical bar g(lum)vertical bar, of 0.2 and 0.1, respectively, which are comparable to those reported for rare-earth chiral complexes. Photophysical properties also revealed an extremely long excited-state lifetime of 1.2 ms and a high quantum yield of 5.2% at room temperature in water. These properties make [Cr(dqp)(2)](3+) an ideal sensitizer for the preparation of enantiopure luminescent supramolecular energy-converting devices and also open up the possibility of using chiral Cr(III) chromophores for the construction of NIR-CPL materials and polarized photonic devices based on earth-abundant metals.

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Green accepted