Self-Assembly of Tetraphenol and Its Complexes with Aromatic Diamines:  Novel Interpenetrating and Noninterpenetrating Organic Assemblies

Abstract

The solid-state self-assembly of tetraphenol 1 and its complexes with 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (bpy-ethe), and 1,2-bis(4-pyridyl)ethane (bpy-etha) is reported. Forces such as O-H‚‚‚N, O-H‚‚‚O and weak interactions prevalent in the structures promote the formation of interpenetrating and noninterpenetrating supramolecular assemblies. The crystal structure of tetraphenol 1 is characterized by the formation of hydrogen-bonded eight-membered cyclic structures. A diamondoid network was observed in the crystal lattice of 1‚bpy with tetraphenol as the node and 4,4′-bipyridine as the spacer. The resulting superadamantane framework is filled via self-clathration to give an 8-fold interpenetrating network. 1‚bpy-ethe self-assembled into a stepladder-type arrangement with the bpy-ethe linkers forming the rungs of the ladder. In the lattice of complex 1‚bpy-etha, ladder-type and cyclic structures organized adjacent to each other and the water molecules present inside the lattice stabilized the assembly through hydrogen bonding. No interpenetrating networks were observed in the lattices of 1‚bpy-ethe and 1‚bpy-etha. The C 3 symmetry of tetraphenol 1, orientation of the -OH groups, and the rigidity or the flexibility of the linking aza compounds together with the interplay of hydrogen bonds and packing forces facilitate the formation of stable supramolecular architectures.

Formation of Interesting Organic Supramolecular Structures in the Solid-State Self-Assembly of Triphenol Adducts

“…Triphenol 1 crystallizes into ladder-type networks held together by O−H···O hydrogen bonds (Figure a). The packing of the molecule in 3D is similar to the previously reported trisphenols 10a. The lattice of 1·pyz is characterized by a ladder structure formed via the interplay of C−H···O and O−H···N bonds.…”

“…Synthesis. A previously reported procedure was used for the synthesis of target triphenol 1 . The synthetic route is shown in Scheme .…”

“…Molecules with C 3 symmetry represent useful materials for studies relating to host−guest complexation and nonlinear optics. 1b, Recently, the solid-state self-assembly of polyphenols that possess C 3 symmetry has been reported in detail by us …”

“…The purpose of the study was to design and synthesize a series of related compounds whose chemical structure could be modified systematically to utilize the strength and directionality of the hydroxyl groups to generate interesting supramolecular structures. Based on the above rationale, the supramolecular organization in 3D triphenols, tetraphenol, and pentaphenol was investigated . The triphenols having hydroxyl groups meta and para to the tertiary carbon atom self-assemble into helical and ladder-type architectures.…”

Isomerism and interpenetration in hydrogen-bonded network structures

“…2 Although many of the interpenetrated structures that have been reported involve metal-organic frameworks, there are also examples involving hydrogen bonded networks. [3][4][5][6] The assembly of solid state structures through hydrogen bonds is an extremely topical area of chemistry. 7 In one of the best illustrations of crystal engineering, Ward and co-workers have shown that guanidinium cations and sulfonate anions assemble through hydrogen bonds into hexagonal sheets, 8,9 and by using disulfonates these sheets can be connected into three-dimensional arrays with predictable structures.…”