Synthetic Strategies toward Higher Cocrystals of Some Resorcinols

Abstract

Higher cocrystal synthesis depends on precise strategic approaches. A total of 32 stoichiometric ternary and quaternary cocrystals based on resorcinol derivatives were achieved using structural inequivalence and shape–size mimicry approaches and are reported here. Along with 28 binary precursors that were also obtained, these 60 cocrystals serve to generalize synthetic strategies toward these ends. A number of large synthon Aufbau modules (LSAMs) were designed depending on the substitution pattern in the resorcinol. The LSAMs from 5-substituted resorcinol were found to be useful in designing higher cocrystals. The construction of a stoichiometric quaternary cocrystal without the “special” compound 2,3,5,6-tetramethylpyrazine has been finally secured.

Structural Variability in Cocrystals: Occurrence of Variable Stoichiometry and High Z′ Forms in a Cocrystal System

“…40−42 This may be due to the larger distance between two −OH groups in DHN. To get a detailed insight into the cocrystal-forming behavior of DHN, a database analysis was performed which resulted in a total of 36 cocrystals (including solvates or hydrates), out of which 23 and 1:2 (VUZCIC and VUZCOI) stoichiometries were observed, 43 while the cocrystal system of DHN: 2,3,5,6tetramethylpyrazine showed the presence of four variable stoichiometries (1:2 (CUBBAD), 44 1:1 (CEXKUP), 45 3:4 (CEXKEZ), 45 and 3:2(CEXLAW) 45 ). To investigate it further, we chose acridine (ACR) as the coformer, mainly due to its conformational rigidity and potential to form the robust O− H•••N with DHN.…”

Anticooperativity and Competition in Some Cocrystals Featuring Iodine‐Nitrogen Halogen Bonds

“…In the field of cocrystal engineering, the relationship between halogen bonds and the possibility of polymorphism and stoichiomorphism are of particular interest [4,5,6,7,8,9,10] . A related area of study is the role of halogen bonds, among other non‐covalent interactions, in generating ternary, quaternary, and higher‐order cocrystals with particular properties or applications [11,12,13,14,15] . Several routes exist towards exploring the polymorphic and stoichiomorphic landscapes of particular cocrystalline systems.…”

“…[4,5,6,7,8,9,10] A related area of study is the role of halogen bonds, among other non-covalent interactions, in generating ternary, quaternary, and higher-order cocrystals with particular properties or applications. [11,12,13,14,15] Several routes exist towards exploring the polymorphic and stoichiomorphic landscapes of particular cocrystalline systems. These include, for example, the use of a variety of cocrystal preparation methods including various slow evaporation approaches, mechanochemistry including ball mill-ing or gentle grinding with a mortar and pestle, and cosublimation.…”

Continuous Making, Stretch Breaking, and Exciton Dynamics of a Red-Emissive Organic Submicrometer-Sized Triangular Pyramid

“…Effective manipulation of intermolecular noncovalent interactions is crucial to attain unique nanostructures. − The hydrophobic–hydrophilic balance thus dictates the nature of ordering of structures. − Striking a such balance is being done by ticking the functional groups of monomers. Among the hydrophilic interactions, hydrogen bonding that is formed by the localized hydroxyl groups of monomers induced by temperature and pH of the medium offers a greater degree of control to tune the morphology vis-a-vis photonic properties of self-assembly. − Hydrogen-bonded self-assembled nanostructures are omnipresent in living systems such as native protein, helical DNA, cellulosic fibers, and other derived structures. − Inspired by their monomer structures, we have selected a natural product, pyrogallol as a precursor in synthesis of fluorescent monomer because it consists of localized hydroxyl groups that are capable of rapidly and robustly forming hydrogen bonds. − …”