Push‐pull dibenzodioxins with electron withdrawing and donating groups were prepared in good yields through a short and simple synthesis. Strong green emission above 500 nm occurs in those derivatives where there is maximum charge transfer to the most electron deficit terephthalonitrile ring, from proximal cyclic amino donor groups. Theoretical calculations support experimental findings through evaluation of excited state properties. In molecules with a nitro group, the excited state localizes electron density exclusively onto it and twisted nitro geometry was also found. In effect, electronic charge cannot relocate into the molecular plane, rendering them non‐fluorescent. Also, studies on the fluorescent derivatives show that best emission would occur when the donor moiety contains a saturated cyclic amino ring and the amines are 2°. Overall, our study establishes structure‐property guidelines and limits on dibenzodioxin functionalization towards preparing fluorescent derivatives of the same.
We have synthesized a small library of blue‐to‐green emissive single benzene‐based fluorophores (SBFs) in a short synthetic sequence. The molecules exhibit good Stokes shift in the range of 60–110 nm and select examples also possess very high fluorescence quantum yields of up to 87%. Theoretical investigations into the ground state and excited state geometries of many of these compounds reveal that good degree of planarization between the electron donor secondary amines and electron accepting benzodinitrile units can be achieved under certain solvatochromic conditions, giving rise to the strongly fluorescent behavior. On the other hand, the excited state geometry which lacks co‐planarity of the donor amine and the single benzene moiety can open up a non‐fluorescent channel. Additionally, in molecules with a dinitrobenzene acceptor, the perpendicular nitro moieties render the molecules completely non‐emissive.
A series of dibenzodioxins containing electron push-pull groups were synthesized using simple methods and their spectroscopic and redox behavior was studied. Electrochemical experiments were performed to measure the redox potentials of the substituted dibenzodioxins. The role of individual molecular subunits in tweaking the redox potential values was delineated by comparing them with the electrochemical properties of analogous heteroacenes. In many cases, our redox potentials were found to be comparably low with that of many wellknown heteroacenes.
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