Notably, the observed thermo-responsive behavior can be attributed not only to thermal motion-induced luminescence quenching, which generally affects emission intensity, but also to the potential effect of phenyl rotations on the symmetry of the complexes, which should impact the luminescence dissymmetry factor values. In this case, the combination of molecular rotational and librational motions within the 1-R and 1-S structures may result in the appearance of temporary conformations with symmetry higher than C2. Such rotation-induced symmetry alteration may be capable of changing and controlling glum values. Our findings demonstrate the correlation between molecular rotation, molecular symmetry, and solid-state chiroptical properties, such as CPL. These insights into the control of CPL properties through molecular rotation are expected to be valuable for the development of new generations of stimuli-responsive solid-state chiroptical materials.