New complexes of Zn(II), Pd(II) and Pt(II) with Schiff bases are prepared in a one-step condensation of 4-(dibutylamino)-2-hydroxybenzaldehyde and 4,5-diaminophthalonitrile in the presence of a metal salt. The complexes possess efficient absorption in the blue-green part of the spectrum with molar absorption coefficients up to 98 000 M⁻¹ cm⁻¹. The Pt(II) complex shows very strong red phosphorescence in anoxic solutions at room temperature with a quantum yield of 65% in toluene which places it among the brightest emitters available for this spectral range. The phosphorescence of the Pd(II) complex under the same conditions is very weak (Φ < 1%) but is enhanced to Φ > 10% upon immobilization into polymers. Optical thermometers based on self-referenced lifetime read-out are prepared upon immobilization of the dyes into gas-blocking poly(vinylidene chloride-co-acrylonitrile). At 25 °C, the materials based on Pd(II) and Pt(II) complexes show sensitivities of −2.1 and −0.52%τ/K, respectively. Application of the sensors for imaging of temperature on surfaces (planar optode) and for monitoring of fast temperature fluctuations (fiber-optic microsensor) is demonstrated. Immobilized into a gas-permeable matrix, the Pt(II) complex also performs as a promising oxygen-sensing material. The new systems are also attractive for imaging of oxygen or temperature with the help of multi-photon microscopy, due to a good match with the biological optical window and much better brightness under two photon excitation compared to that of the conventional Pt(II) meso-tetra-(pentafluorophenyl)porphyrin.