Functional group induced excited state intramolecular proton transfer process in 4-amino-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester: a combined spectroscopic and density functional theory study.

The molecule methyl-2-aminonicotinate (2-MAN) does not exhibit excited state intramolecular proton transfer (ESIPT), but its derivative 4-amino-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester (AMPCE), widely used in the preparation of pyrimidopyrimidines as a protein kinase inhibitor, does exhibit ESIPT. Increasing acidic and basic character at the proton donor and proton acceptor sites by adding functional groups is found to be responsible for the large Stokes shifted ESIPT emission (Δν = 12,706 cm(-1)) in AMPCE. The photophysics of AMPCE have been explored on the basis of steady state and time resolved spectral measurements, quantum yield calculation with variation of polarity, as well as hydrogen bonding ability of solvents. Experimental findings have been correlated with the calculated structure and potential energy surfaces based on the intramolecular proton transfer model obtained by density functional theory (DFT). Properties based on the calculated excited state surfaces generated in vacuo and methanol solvent using time dependent density functional theory (TDDFT) and time dependent density functional theory polarized continuum model (TDDFT-PCM), respectively, show good agreement with the experimental findings. HOMO and LUMO diagrams also support the favorable ESIPT process in the first excited state potential energy surface.