1,10-Phenanthrolines with Tunable Luminescence upon Protonation:  A Spectroscopic and Computational Study

We have synthesized nine 2,9-aryl-substituted 1,10-phenanthrolines (1−9) with the aim of rationalizing their electronic absorption and luminescence properties in both the basic and acid form. The latter are generated upon addition of trifluoroacetic acid to CH2Cl2 solutions of 1−9 and their formation is unambiguously evidenced by UV−vis absorption and 1H NMR spectroscopy. 1−9 can be subdivided into three groups, depending on their chemical structure and luminescence behavior. 1−3 are symmetrically substituted p-dianisylphenanthrolines which exhibit relatively intense violet fluorescence in CH2Cl2 (λmax ca. 400 nm, Φfl = 0.12−0.33) and are strongly quenched and substantially red-shifted upon protonation (λmax ca. 550 nm, Φfl = 0.010−0.045). 4−5 are 2,6-dimethoxyphenylphenanthrolines with faint luminescence in both the basic and acid form. 6−9 are various unsymmetric aryl-substituted-phenanthrolines and their relatively strong fluorescence (λmax ca. 400 nm, Φfl = 0.08−0.24) is red-shifted and substantially enhanced following protonation (λmax ca. 475 nm, Φfl = 0.16−0.50). The markedly different trends in the electronic absorption and fluorescence spectra are rationalized by means of both time-dependent Hartree−Fock and density functional theory by using hybrid functionals to assign the excited states. Interestingly, protonation of 1−9 also occurs in spin-coated films simply exposed to vapors of acid, and the reaction can be signaled by the color tuning of the emission signal (vapoluminescence). This observation makes substituted phenanthrolines potential candidates as proton sensors also in the solid phase.