The new luminescent carbonyl compounds [Mn(Oxa-H)(CO)(3)Br] (1) and [Mn(Oxa-NMe2)(CO)(3)Br] (2) were synthesized and fully characterized. Complexes 1 and 2 showed CO release under blue light (lambda(453)). Spectroscopic techniques and TD-DFT and SOC-TD-DFT calculations indicated that 1 and 2 release the Oxa-H and Oxa-NMe2 coligands in addition to the carbonyl ligands, increasing the luminescence during photo-induction.