The rational assembly of monomers, in principle, enables the design of a
specific periodicity of polymeric frameworks, leading to a tailored set of
electronic structure properties in these solid-state materials. The further
development of these emerging systems requires a combination of both
experimental and theoretical studies. Here, we investigated the electronic
structures of two-dimensional polymeric frameworks based on triazine and
benzene rings, by means of electrochemical techniques. The experimental density
of states was obtained from quasi-open-circuit voltage measurements through
galvanostatic intermittent titration technique, which we show to be in
excellent agreement with first principles calculations performed for two and
three-dimensional structures of these polymeric frameworks. These findings
suggest that the electronic properties do not only depend on the number of
stacked layers but also on the ratio of the different aromatic rings
