The synthesis and crystal structure of rhodamine 590 acid phthalate (RhAP) have been reported. This novel solid-state rhodamine derivative not only has a longer fluorescence lifetime compared to rhodamine solid-state matrixes where emission is quenched but also possesses strong nonlinear optical characteristics. The static and dynamic first- and second-order hyperpolarizabilities were calculated using the time-dependent density functional theory at the B3LYP/6-31+G* level. The computed static values of β and γ of RhAP by the X-ray diffraction (XRD) structure were 31.9 × 10-30 and 199.0 × 10-36 esu, respectively. These values were about 62 times larger than the corresponding values in urea, an already well-known nonlinear optical material. The second-order hyperpolarizability of the compound was determined experimentally by measuring the two-photon absorption cross section using intensity-modulated light fields. The reported compound, excitable at near-infrared, exhibited frequency upconversion with the two-photon absorption coefficient enhanced by two orders of magnitude compared to that of the dye solution. Hosting the dye in the solid, at high concentrations, exploits the nonlinearity of the dye itself as well as results in significant excitonic effects including formation of broad exciton band and superradiance.

Organic laser dyes Coumarin 485, Coumarin 540 and Rhodamine 590 Chloride were used to dope potassium acid phthalate crystals (KAP). Dye-doped KAP crystals with different dye concentrations such as 0.01 mM, 0.03 mM, 0.05 mM, 0.07 mM and 0.09 mM (in the KAP growth solution) were grown. The linear optical, non-linear optical, mechanical and thermal characterizations of dye-doped KAP crystals were studied and compared to understand the effect of dye and dye concentration on the KAP crystal. Absorption and emission studies of KAP and dye-doped KAP single crystals indicated the inclusion of the dye into the KAP crystal lattice. The effect of dye and its concentration on the SHG efficiency of the KAP crystal was studied using the Kurtz and Perry powder technique. It was observed that the absorption maximum wavelength and concentration of the dye used for doping the KAP single crystal decided the SHG efficiency of the dye-doped KAP single crystals. The mechanical hardness of the dye-doped and undoped (pure) KAP single crystals were studied using the Vickner’s microhardness test. It was observed that doping the KAP crystals with the laser dyes changed them from softer material to harder material. Etching studies showed an improvement in the optical quality of the KAP crystal after doping with laser dyes.