Linear fitting of the measured (001) spacings over the number of carbon atoms in the pillars' alkyl-chains demonstrates positive correlation (Fig. ). The arrangement of alkyldiamine pillars within the V2O5 host structure is approximated by geometrical considerations (Fig. , inset), in accordance with previous work on pillared layered/2D materials. These approximations base on the assumptions that (1) most alkyldiamines interact with V2O5 bilayers at both opposing sides of the interlayer galleries via their functional amine/ammonium groups, i.e., form "bridges" between the layers as described for insertion of alkyldiamines into clays under acidic conditions. An in-depth correlative microscopy investigation of the synthesized samples with variable nanoconfinement geometry is undertaken to elucidate the pillar-induced changes in the host structure. Scanning and transmission electron microscopy (SEM and TEM) are leveraged to confirm the materials' homogeneity, to gain insights into their morphology, to assess crystallinity and to verify the crystal structure (Fig. ). All the molecularly pillared samples (V2O5-2C-DA, V2O5-6C-DA and V2O5-12C-DA) show characteristic nanowhisker morphology (SEM: Fig. , TEM: Fig. ), allowing for individual free-standing strands to be investigated further. The V2O5-12C-DA system shows stronger bundling/agglomeration of the whiskers (Fig. and) compared to V2O5-2C-DA and V2O5-6C-DA, which is attributed to the solvent modification (ethanol-water mixture instead of only water, which is necessary to adequately dissolve 1,12-dodecanediamine). 48,49 TEM bright-field imaging (Fig. ) verifies the sample homogeneity and single-crystalline nature of the whiskers with low defect density.