A new mixed pyridyl-carboxylate ligand with two picolinate chromophores and a flexible linear spacer, potassium 2,2'-(butane-1,4-diylbis((pyridin-2-ylmethyl)azanediyl))diacetate (Kbpbd), which is obtained in high yield and spectroscopically characterized, has been utilized to make new lanthanide complexes, namely, [Ln(bpbd) (HO)(NO)]·HO, where Ln = Tb () and = 6, Ln = Sm () and = 7, and Ln = Dy () and = 7. These complexes have been extensively characterized by various spectroscopic techniques (UV-vis and Fourier transform infrared spectroscopy), elemental analyses, thermogravimetric analysis, field emission scanning electron microscopy, and powder X-ray diffraction. These show very intense characteristic luminescence features that confirm the antenna effect of the ligand on the metal center. These complexes have been utilized for the detection of various nitroaromatic compounds. Among these three complexes, is found to be the best for the selective sensing of 2,4,6-trinitrophenol in water with a detection limit of (0.35 ± 0.05) ppm. Its Stern-Volmer constant, [(5.48 ± 0.1) × 10 M], is one of the highest among similar sensors reported so far.