As molecules with emission properties in the NIR region are highly intriguing, we examined the NLO response of molecules (1-3) with D-π-A-π-D architecture (Figure ). The ground state geometry of these molecules were optimized, followed by computation of their first hyperpolarizability. Before computing their NLO response properties, the one-photon absorption of these molecules were studied using time-dependent density functional theory (TDDFT)to find out the best basis set/functional combination. Several functional including B3LYP, PBE1PBE, CAM-B3LYP, ωB97XD, and ω*B97XD, with a 6-31G(d) basis set were used to study the absorption of the aforesaid molecules (Table and). Our analysis revealed that the tuned functional exhibited minimal divergence from the experimental absorption values. As the NLO properties of quadrupolar molecules with D-π-A π-D framework were not much satisfying (see Table and), presumably due to their Centrosymmetric nature, basic molecular structure modifications to D-π-A were made, which helped us to greatly enhance the NLO response of the molecules. The ICT is an important factor which affects the NLO properties of organic molecules.