Two new crystallographically characterized samarium complexes, [Sm(fod)3(L1)] (1) and [Sm(fod)3(L2)] (2) {L1 = 4,7-diphenyl-1,10-phenanthroline (bath), L2 = 2,2':6',2''-terpyridine and fod = anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione (Hfod)}, were synthesized and thoroughly characterized. Single-crystal (SC) analysis shows that complex 1 is an eight-coordinate structure with a distorted square antiprism geometry (D4d), whereas complex 2 possesses a nine-coordinate structure with distorted muffin geometry (Cs). The NMR results are in line with SC-XRD analysis, which further validate that the complexes remain intact in solutions. The photophysical characteristics of the complexes were studied in both visible and near infra-red (NIR) regions. The PLQY values of the present complexes were found to be higher than those reported in the literature except for a tetrakis Sm complex. This result indicates that both the ligands act as effective antennas for the present systems. A comparison of PLQY and emission lifetime values within the present complexes (in solid state) reveals that energy transfer from terpy to Sm3+ is more effective than that from the bath ligand. Various color parameters of the complexes were calculated, and the determined CCT values suggest that the complexes may be used as warm light sources. The determined band gap values for the complexes are in the range of those for semiconductors, which suggest the application of present systems in the field of optoelectronics. The curve between the emission intensity and temperature for complex 1 shows a perfect linearity (χ2 = 0.99), which suggests that this complex can have potential application as a temperature sensor in the range 60-350 K.