Rational design and first-principles studies toward the remote substituent effects on a novel tetracyclic proton sponge

According to reliable density functional theory (DFT) calculations, 11,12-dimethyl-11,12-diazatetracyclo[6.2.1.1(3,6).0(2,7)]dodecane derivatives have been predicted as superorganic bases in the gas phase, acetonitrile, and the aqueous phase. The basicities of these tetracyclic proton sponges were modulated through remote substituent effects. Barriers for proton transfer between the N atoms of the diamine cations are also reported.