Fig. 3. (a) Schematic illustration of molecular models probing the relative orientation and interlayer distance of the spacer moiety with respect to the imine bond configuration in a condensed framework. The antiparallel EE model combines the least steric repulsion of the methyl groups with best π overlap. (b) Experimental pair distribution function (PDF) for m₂₀-COF and simulated PDFs with different values of the displacement parameter U₃₃, simulating the effects of stacking and conformational disorder, are overlaid. (c) Interlayer density distributions simulated for different layer offset scenarios in 2D honeycomb layered COFs are shown to demonstrate the specific impact of different relative stacking offsets on the PDF profile (U₁₁ = U₂₂ = 1.0 Ų; U₃₃ = 0.05 Ų).