New coumarin fluorescent based D-π-A-π-D dyes are synthesized and studied for their optical properties. Their show absorption and emission respectively are in the range of 471–504 nm and 506–550 nm. Viscosity induced emission intensity increase is examined with 0–100% PEG-400 in ethanol MLK 4 is good FMR as compared to the MLK 1–3 due to the presence of extra-π-conjugation. FMO analysis and Generalized Mulliken Hush analysis show a strong interaction of molecular charge transfer characteristics. The first (α), second (β) and third (γ) order polarizability of MLK 1–4 are calculated by the solvatochromic technique and corroborated by DFT calculations using CAM-B3LYP/6-31G(d) method. The outcomes found by solvatochromic technique are compared theoretically with DFT using B3LYP/6-31G(d) and CAM-B3LYP/6-31G(d) methods. These methods reveal that, CAM-B3LYP/6-31G(d) carry out for calculating α, β, γ. Photophysical data was also applied to establish the ground and excited state dipole moment ratio using Bakhshiev, Bilot-Kawski, and Liptay functions. Liptay function shows better correlations than the other two functions for all dyes.