Diaminotriazinyl-Functionalized Oligopyridine Mimics: From Crystal Engineering to DNA and Enzyme Docking

Abstract

The design of molecular tectoligands capable of combining coordination and supramolecular recognition properties is of considerable interest for crystal engineering. Herein, we report the synthesis of four new diaminotriazinyl-functionalized oligopyridine mimics, Py2DAT, PyDAT2, m-qtpy, and m-qpy, obtained in excellent yields (>90%) through a simple and efficient synthetic strategy. These compounds were conceived as structural analogues of classical oligopyridines in which selected pyridine units are replaced by diaminotriazinyl (DAT) groups, introducing complementary hydrogen-bond donor and acceptor sites. Comprehensive characterization by NMR, Fourier transform infrared spectroscopy (FTIR), HRMS, ultraviolet–visible (UV–vis) spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction confirmed the structures and revealed remarkable supramolecular organization in the solid state. The DAT groups act as robust supramolecular synthons, directing self-assembly through predictable N–H···N hydrogen-bonding interactions involving both DAT and pyridyl nitrogen atoms. Depending on the molecular topology, the compounds generate crystal architectures ranging from discrete dimers to two-dimensional networks, bilayer assemblies, and ribbon-like structures. The progressive incorporation of DAT units enables precise modulation of molecular geometry, hydrogen-bonding motifs, and crystal packing. These DAT-functionalized oligopyridine mimics constitute a new family of multifunctional building blocks combining hydrogen-bonding motifs with oligopyridine-like coordination sites, making them promising candidates for future coordination-driven supramolecular architectures. Preliminary docking studies further indicate favorable molecular recognition toward DNA and enzyme targets, highlighting the multifunctional character of these bioinspired building blocks.