Synthesis and Structural Studies of Three-Dimensional Supramolecular Motifs Derived from Neutral and Cationic Zinc Alkanesulfonates (original) (raw)
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Coordination motifs in modern supramolecular chemistry
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Journal of Pharmacy and Pharmacology Research, 2023
Supramolecular chemistry is a captivating and interdisciplinary field that explores the interactions between molecules to form complex and functional assemblies through non-covalent forces. This review paper presents an indepth exploration of the fundamental concepts, supramolecular assemblies and structures, applications in nanotechnology and biology, as well as challenges and future perspectives in supramolecular chemistry. The paper begins by elucidating the fundamental principles of supramolecular chemistry, emphasizing the significance of weak, non-covalent interactions such as hydrogen bonding, van der Waals forces, and π-π interactions. Molecular recognition, self-assembly, and host-guest interactions are highlighted as key concepts shaping the field. Subsequently, the review delves into various supramolecular assemblies and structures, showcasing the diversity of nanoscale architectures that arise from self-assembly processes. From nanotubes and nanofibers to metal-organic frameworks and dynamic supramolecular systems, each structure's properties and potential applications are explored. The application of supramolecular chemistry in nanotechnology and biology is a central focus of the paper. It covers the design of supramolecular materials for drug delivery, nanoelectronics, nanosensors, and biomimetic systems. Additionally, the integration of supramolecular approaches in biology, including molecular recognition, enzyme mimics, and bioimaging, is discussed in detail. Furthermore, the challenges faced by supramolecular chemistry, such as predictability, stability, and scalability, are addressed. The paper also looks into the future perspectives of the field, envisioning adaptive materials, supramolecular machines, and data-driven design as exciting prospects. Overall, this comprehensive review offers a thorough understanding of the captivating world of supramolecular chemistry and its potential to revolutionize various scientific and technological domains. Through interdisciplinary efforts and a focus on sustainability, supramolecular chemistry holds promise for addressing real-world challenges and shaping a future defined by innovative materials and transformative applications.
IUCrJ, 2018
In order to develop transferable and practical avenues for the assembly of coordination complexes into architectures with specific dimensionality, a strategy utilizing ligands capable of simultaneous metal coordination and self-complementary hydrogen bonding is presented. The three ligands used, 2(1H)-pyrazinone, 4(3H)-pyrimidinone and 4(3H)-quinazolinone, consistently deliver the required synthetic vectors in a series of CdII coordination polymers, allowing for reproducible supramolecular synthesis that is insensitive to the different steric and geometric demands from potentially disruptive counterions. In all nine crystallographically characterized compounds presented here, directional intermolecular N-H⋯O hydrogen bonds between ligands on adjacent complex building blocks drive the assembly and orientation of discrete building blocks into largely predictable topologies. Furthermore, whether the solids are prepared from solution or through liquid-assisted grinding, the structural o...
Unravelling the Growth of Supramolecular Metal–Organic Frameworks Based on Metal-Nucleobase Entities
Crystal Growth & Design, 2015
The present work provides the basis to obtain three-dimensional (3D) extended porous supramolecular assemblies named supramolecular metal−organic frameworks (SMOFs). This goal can be achieved by considering three key factors: (i) the use of rigid building units, (ii) the establishment of predictable and rigid synthons between the building units, and (iii) the non-coplanarity of functional groups involved in the predictable synthons. Throughout this report we demonstrate the suitability of this synthetic strategy supported by six new SMOFs based on metal-nucleobase entities which fulfill the stated requirements: [Co(ThioG) 3 ] (SMOF-4; ThioG = thioguaninato), [Co(Hade) 2 X 2 ] (SMOF-5, SMOF-6; Hade = adenine and X = Cl − , Br − ), [Cu 8 (μ 3 -3 OH)] n (SMOF-9). SMOF-4 is built up from monomeric entities in which bidentate thioguaninato ligands establish complementary hydrogen bonding interactions in non-coplanar directions leading to supramolecular layers that are further connected resulting in a porous structure with one-dimensional (1D) channels. The hydrogen bonding interactions among Watson−Crick and sugar edges of monomeric entities in SMOF-5 give rise to a triply interpenetrated supramolecular framework. Octameric clusters in SMOF-7 are self-assembled by hydrogen bonding to yield a porous 3D network. SMOF-8 is built up from tetranuclear units that are linked via base pairing interactions involving Watson−Crick faces to afford layers whose assembly generates a twodimensional pore system. SMOF-9 is in between pure MOFs and SMOFs since it consists of 1D infinite coordination polymers held together by complementary hydrogen bonding interactions into a 3D supramolecular porous structure. Figure 1. Similarity between (a) coordination bonds and (b) hydrogen bonding interactions as structure directing agents. Article pubs.acs.org/crystal
Towards Building Blocks for Supramolecular Architectures Based on Azacryptates
Molecules, 2020
In this work, we report the synthesis of a new bis(tris(2-aminoethyl)amine) azacryptand L with triphenyl spacers. The binding properties of its dicopper complex for aromatic dicarboxylate anions (as TBA salts) were investigated, with the aim to obtain potential building blocks for supramolecular structures like rotaxanes and pseudo-rotaxanes. As expected, UV-Vis and emission studies of [Cu 2 L] 4+ in water/acetonitrile mixture (pH = 7) showed a high affinity for biphenyl-4,4-dicarboxylate (dfc 2−), with a binding constant of 5.46 log units, due to the best match of the anion bite with the Cu(II)-Cu(II) distance in the cage's cavity. Compared to other similar bistren cages, the difference of the affinity of [Cu 2 L] 4+ for the tested anions was not so pronounced: conformational changes of L seem to promote a good interaction with both long (e.g., dfc 2−) and short anions (e.g., terephthalate). The good affinity of [Cu 2 L] 4+ for these dicarboxylates, together with hydrophobic interactions within the cage's cavity, may promote the self-assembly of a stable 1:1 complex in water mixture. These results represent a good starting point for the application of these molecular systems as building units for the design of new supramolecular architectures based on non-covalent interactions, which could be of interest in all fields related to supramolecular devices.
Design, syntheses, and crystal engineering of versatile supramolecular reagents
2005
Crystal engineering, or non-covalent synthesis in the solid state, requires an understanding of intermolecular forces, and the hydrogen bond has become a reliable non-covalent tool in the construction of supramolecular architectures. In the same way that synthetic chemists refer to a "yield" to quantify a desired product, crystal engineers typically determine the successful formation of a supramolecular product according to the frequency or occurrence of preferred intermolecular interactions between molecules under certain reaction conditions, thus, the supramolecular yield. These non-covalent reactions can be effectively carried out using supramolecular reagents (SR's). A family of ditopic bis-imidazol-1-yl/benzimidazol-1-yl compounds were synthesized and used as SR's in combination with a variety of dicarboxylic acids to produce binary solids in 100% yield through the primary acid•••imidazol-1-yl/benzimidazol-1-yl synthons even in the presence of potentially disruptive intermolecular interactions. We furthermore noted that secondary C-H•••O interactions within and between 1-D chains were of equal structural importance based upon an analysis of the metrics displayed by these interactions. The use of these SR's as ligands with neutrally charged metal complexes was also investigated. SR's containing benzimidazol-1-yl and carboxamide moieties were synthesized and combined with two different carboxylic acids to make ternary solids through acid•••benzimidazol-1-yl and carboxamide•••acid hydrogen bonds using a hierarchical approach-the best donor-best acceptor, second best donor-second best acceptor guidelines. These SR's were also employed as ligands for high-yielding syntheses of linear metal complexes where neighboring complexes are linked via carboxamide•••carboxamide hydrogen bonds. Asymmetric SR's possessing two different N-heterocycles were synthesized and employed in the construction of ternary supermolecules with a high degree of structural selectivity and specificity when introduced to two different carboxylic acids. The stronger acid interacts at the more basic site, while the weaker acid hydrogen-bonds with the less basic nitrogen atom. Finally, an SR containing three different binding sites was designed and synthesized with the aim of producing quaternary co-crystals.