Augmentation of NIR Circularly Polarized Luminescence Activity in Shibasaki-Type Lanthanide Complexes Supported by the Spirane Sphenol.

Abstract

We report two new circularly polarized luminescence (CPL)-active lanthanide complexes emissive in the near-infrared (NIR) region; using sphenol as a supporting ligand, we provide the first reported example of an NIR-emissive lanthanide complex supported by a chiral spirane. Inclusion of a quaternary carbon to impart axial chirality results in dramatic augmentation of the CPL strength of the resultant sphenolate complexes (glum ≤ 0.77 for [(sphenol)3ErNa3(thf)6]) compared to that of their contemporary biaryl-based axially chiral analogues (glum ≤ 0.47 for [(binol)3ErNa3(thf)6]). Despite similar structural parameters, the rigid spiro carbon of sphenol enables the strongest dissymmetry factors observed to date from Shibasaki-type complexes for both Yb and Er. We also demonstrate the sensitivity of the reported chiroptical measurements to small variations in instrumental parameters, such as bandpass, and suggest a standardized method or at least that additional detail should be included in future reports to allow for direct comparisons between newly published CPL emitters.