Piezo-Responsive Hydrogen-Bonded Frameworks Based on Vanillin-Barbiturate Conjugates

A concept of piezo-responsive hydrogen-bonded π-π-stacked organic frameworks made from Knoevenagel-condensed vanillin–barbiturate conjugates was proposed. Replacement of the substituent at the ether oxygen atom of the vanillin moiety from methyl (compound 3a) to ethyl (compound 3b) changed the appearance of the products from rigid rods to porous structures according to optical microscopy and scanning electron microscopy (SEM), and led to a decrease in the degree of crystallinity of corresponding powders according to X-ray diffractometry (XRD). Quantum chemical calculations of possible dimer models of vanillin–barbiturate conjugates using density functional theory (DFT) revealed that π-π stacking between aryl rings of the vanillin moiety stabilized the dimer to a greater extent than hydrogen bonding between carbonyl oxygen atoms and amide hydrogen atoms. According to piezoresponse force microscopy (PFM), there was a notable decrease in the vertical piezo-coefficient upon transition from rigid rods of compound 3a to irregular-shaped aggregates of compound 3b (average values of d33 coefficient corresponded to 2.74 ± 0.54 pm/V and 0.57 ± 0.11 pm/V), which is comparable to that of lithium niobate (d33 coefficient was 7 pm/V). © 2022 by the authors.2.1.06.03, 20211572; Russian Foundation for Basic Research, РФФИ: 20-53-00043-Bel_a; Ministry of Science and Technology, Taiwan, MOST: 19-52-06004 MNTI_a; Ural Federal University, UrFU: 2968; Ministry of Science and Higher Education of the Russian Federation: 075-15-2021-677The work was supported by the Russian Foundation for Basic Research (RFBR, project no. 20-53-00043-Bel_a) and the PFM measurements were done under RFBR and MOST project no. 19-52-06004 MNTI_a. The equipment of the Ural Center for Shared Use “Modern nanotechnology” Ural Federal University (Reg. No. 2968), which is supported by the Ministry of Science and Higher Education RF (project No. 075-15-2021-677), was used. T.V.S. acknowledges the support from the State Program of Scientific Researchers of Belarus (research issue 2.1.06.03, state registration number: 20211572)