Programmed Molecular Construction: Driving the Self-Assembly by Coordination and Hydrogen Bonds Using 6-(Pyridin-2-yl)-1,3,5-triazine-2,4-diamine with M(NO₃)₂ Salts

Abstract

A new series of hydrogen-bonded metallotecton networks 6–9 of the general formula [M( 2 ) 2 (NO 3 ) 2 ] were obtained from the reaction of 6-pyridin-2-yl-[1,3,5]-triazine-2,4-diamine 2 with transition-metal ions [M: Co(II), Ni(II), Cu(II), and Zn(II)]. Their supramolecular networks and associated properties were characterized by single-crystal and powder X-ray diffraction, IR, solid-state UV–vis spectroscopy, and thermogravimetric analysis associated with differential scanning calorimetry. On the basis of standard patterns of coordination involving 2,2′-bipyridine and simple derivatives, compound 2 binds transition-metal ions with predictable constitution and the diaminotriazinyl (DAT) groups serve orthogonally to ensure the intermetallotecton interactions by hydrogen bonding according to well-established motifs I–III . As expected, compound 2 formed octahedral 2:1 metallotectons with M(NO 3 ) 2 , and further self-assembled by hydrogen bonding of the DAT groups to produce pure, crystalline, homogeneous, and thermally stable materials. In these structures, nitrate counterions also play an important role in the cohesion of intermetallotectons to form two-dimensional and three-dimensional networks. These results illustrated the effectiveness of the synthetic approach to create a wide range of novel ordered materials with controllable architectures and tunable properties achieved by varying the central metal ion. Crystal morphologies of 6–9 were also investigated by scanning electron microscopy and calculation using Bravais–Friedel–Donnay–Harker method from their single-crystal structure.

Photocatalytic Carbon Dioxide Reduction and Density Functional Theory Investigation of 2,6-(Pyridin-2-yl)-1,3,5-triazine-2,4-diamine and Its Cobalt and Nickel Complexes

“…It is noteworthy that motif IV has already been reported for association of DAT groups in our previous work. 36,46 The network is reinforced by multiple hydrogen bonds involving ClO 4 − . Summaries of the crystallographic data and hydrogen bonds and angles are provided in Table S1 and Table S2.…”

“…In crystal engineering, 1 is called a tectoligand 35 and 2 and 3 metallotectons. 36,37 They are compounds that can self-assemble to form robust framework hydrogen bonds with reliable patterns. The presence of -NH 2 Lewis basic sites and triazinyl rings (πelectron deficient core) makes them particularly good candidates for the photocatalytic CRR.…”

“…The present work investigated (i) the synthetic method to prepare metal complexes 2 and 3 based on 2,6-(Pyridin-2-yl)-1,3,5-triazine-2,4-diamine 1 , a ligand that mimics tpy (Chart a), (ii) the comparison of their molecular structures with [M­( tpy ) 2 ] x+ , (iii) the study of their association by hydrogen bonds involving DAT groups (Chart b), (iv) their physicochemical properties, (v) their photocatalytic activity for the CO 2 reduction reaction (CRR) to produce CO, and (iv) tracking of the mechanistic pathways. In crystal engineering, 1 is called a tectoligand and 2 and 3 metallotectons. , They are compounds that can self-assemble to form robust framework hydrogen bonds with reliable patterns. The presence of -NH 2 Lewis basic sites and triazinyl rings (π-electron deficient core) makes them particularly good candidates for the photocatalytic CRR.…”

Transformation of the coordination nanostructures of 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid molecules on HOPG triggered by the change in the concentration of metal ions

“…A variety of studies have demonstrated the coordination nanostructures by altering organic ligands, such as carboxylate, 3,5,12,18 hydroxyl, 14,20,21 pyridine, 9,22-25 and triazine. [26][27][28][29][30] The triazine derivatives are important in a range of areas as ligands for supramolecular self-assembly of more complex mixed layers, hence it may be interesting to study the coordination properties of the triazine derivatives. In this article, we fabricated different coordination nanostructures by 4,4 0 ,4 00 -(1,3,5-triazine-2,4,6-triyl) tribenzoic acid (TATB) molecules coordinating with Cu 2+ or Fe 3+ ion with different concentrations on highly oriented pyrolytic graphite (HOPG) surface.…”

Mimicking 2,2′:6′,2′′:6′′,2′′′-quaterpyridine complexes for the light-driven hydrogen evolution reaction: synthesis, structural, thermal and physicochemical characterizations

“…Complexes based on coordination of both unsubstituted and functionalized bipyridine (bpy), terpyridine (tpy) and quaterpyridine (qtpy) with transition metals have been widely studied in particular for the formation of various metallosupramolecular architectures. [1][2][3][4][5][6][7][8] There is very extensive literature concerning polypyridine ligands and their complexes, but a relatively few investigations have been done on functionalized systems, particularly on qtpy. Many interests were focused on qtpy, a tetradentate ligand that can form metal complexes of different geometries.…”