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Diversity in supramolecular chemistry can showcase itself in many ways. This includes the diversity of thought and topics covered in research (from fundamental science to applications in biology and materials), as well as the diversity of people (e.g., diversity in race, gender, sexual orientation, country of origin, type of higher education institute, career stage, ). At the North American Supramolecular Chemistry (NASC) meetings, we aim to bring together the best that supramolecular chemistry has to offer in North America, create a sense of community and provide a platform for researchers at any stage of their career to present their work. NASC 2023 was the successful second edition of the NASC meeting series, and this proceedings article highlights the research and impressions of some of the speakers at NASC 2023.
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Supramolecular macrocyclic forces have been used to trap phytate, myo-inositol-1,2,3,4,5,6-hexakisphosphate, a key bioanion with multiple roles in metabolic processes. Due to the complex chemistry of six multivalent phosphates surrounding the small, cyclic inositol framework, crystallographic information of simple phytate salts has been elusive. This report represents a combined crystallographic, theoretical, and solution binding investigation of a supramolecular macrocyclic complex of phytate. Together, the results provide significant insight to phytate's intramolecular and intermolecular interactions at the microenvironment level. The macrocycle-phytate aggregates consist of phytate anionic pairs, each partly sandwiched by two 24-membered, amide/amine-based cationic macrocycles. The phytate ion pairs hold the tetrameric macrocyclic array together by six strong intermolecular hydrogen bonds. Both phytates crystallize in 1a5e phosphate conformations (one axial (P2) and five equatorial phosphates). Solution NMR binding studies in 1 : 1 DMSO-d6 : D2 O indicate 2 : 1 macrocycle:phytate associations, suggesting that the sandwich-like nature of the complex holds together in solution. DFT studies indicate the likely occurrence of dynamic intramolecular interchange of phosphate protons, as well as important roles for the axial (P2) phosphate in both intramolecular and intermolecular hydrogen bonding interactions.
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Hydrophobic and hydrophilic, monotopic and ditopic carboxamide pincer hosts containing ethyl, hexyl, 2-hydroxyethyl and 2-hydroxyethyl ethyl ether pendant arms were synthesized. Solubility trends indicated that solubilities in water or hydrocarbon solvents varied depending on the nature of the pendant arms. Binding constants for hydrophilic pincers were larger in general than their hydrophobic analogs. Significant synergistic binding effects for the ditopic hosts were not observed.
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Experimental and topological analyses of dipalladium(II) complexes with pyrazinetetracarboxamide ligands containing tetraethyl (1), tetrahexyl (2), and tetrakis(2-hydroxyethyl) ethyl ether (3) are described. The presence of two very short O---O distances between adjacent amide carbonyl groups in the pincer complexes revealed two protons, which necessitated two additional anions to satisfy charge requirements. The results of the crystal structures indicate carbonyl O---O separations approaching that of low barrier hydrogen bonds, ranging from 2.413(5) to 2.430(3) Å. Solution studies and quantum topological analyses, the latter including electron localization function, noncovalent interaction, and Bader's quantum theory of atoms in molecules, were carried out to probe the nature of the short hydrogen bonds and the influence of the ligand environment on their strength. Findings indicated that the ligand field, and, in particular, the counterion at the fourth coordination site, may play a subtle role in determining the degree of covalent association of the bridging protons with one or the other carbonyl groups.
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Tetraethylpyrazine-2,3,5,6-tetracarboxamide forms a dipalladium(II) complex with acetates occupying the fourth coordination sites of the two bound metal ions. Crystallographic results indicate that the "duplex" dipincer has captured two protons that serve as the counterions. The protons lie between adjacent amide carbonyl groups with very short O···O distances of 2.435(5) Å. In the free base, the adjacent carbonyl groups are farther apart, averaging 3.196(3) Å. While the dipalladium(II) complexes stack in an ordered stepwise fashion along the a axis, the free base molecules stack on top of each other, with each pincer rotated by about 60° from the one below.
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The influence of chelate and mini-chelate effects on sulfate binding was explored for six amide-, amide/amine-, urea-, and urea/amine-based ligands. Two of the urea-based hosts were selective for SO4(2-) in water-mixed DMSO-d6 systems. Results indicated that the mini-chelate effect provided by a single urea group with two NH binding sites appears to provide enhanced binding over two amide groups. Furthermore, additional urea binding sites incorporated into the host framework appeared to overcome to some extent competing hydration effects with increasing water content.
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Amidas/química , Quelantes/química , Sulfatos/química , Urea/análogos & derivados , Sitios de Unión , Dimetilsulfóxido/química , Ligandos , Modelos Moleculares , Compuestos de Amonio Cuaternario/química , Agua/químicaRESUMEN
An amine/amide mixed covalent organic tetrahedral cage 1 (H(12)) was synthesized and characterized. The H(12) cage contains 12 amide NH groups plus four tertiary amine N groups, the latter of which are positioned in a pseudo-tetrahedral array. Crystallographic findings indicate that the tetrahedral host can adopt either a pseudo-C(3) symmetric "compressed tetrahedron" structure, or one in which there are two sets of three stacked pyridine units related by a pseudo-S(4) axis. The latter conformation is ideal for encapsulating small pentameric clusters, either a water molecule or a fluoride ion surrounded by a tetrahedral array of water molecules, i.e., H(2)O·4H(2)O or F(-)·4H(2)O, as observed crystallographically. In solution, however, (19)F NMR spectroscopy indicates that H(12) encapsulates fluoride ion through direct amide hydrogen bonding. By collectively combining one-dimensional (1)H, (13)C, and (19)F with two-dimensional (1)H-(1)H COSY, (1)H-(13)C HSQC, and (1)H-(19)F HETCOR NMR techniques, the solution binding mode of fluoride can be ascertained as consisting of four sets of independent structural subunits with C(3) symmetry. A complex deuterium exchange process for the fluoride complex can also be unraveled by multiple NMR techniques.
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Amidas/química , Aminas/química , Hidrógeno/química , Cristalografía por Rayos X , Flúor/química , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Estructura MolecularRESUMEN
Six amide-based NNN palladium(II) pincer complexes Pd(L)(CH3CN) were synthesized, characterized, and examined for binding the sulfur mustard surrogate, 2-chloroethyl ethyl sulfide (CEES). The complexes all bind readily with CEES as shown by (1)H NMR spectroscopy in CDCl3. The influence of para-substituents on the two amide phenyl appendages was explored as well as the effect of replacing the phenyl groups with larger aromatic rings, 1-naphthalene and 9-anthracene. While variations of the para-substituents had only a slight influence on the binding affinities, incorporation of larger aromatic rings resulted in a significant size-related increase in binding, possibly due to increasing steric and electronic interactions. In crystal structures of three CEES-bound complexes, the mustard binds through the sulfur atom and lies along the aromatic walls of the side appendages approximately perpendicular to the pincer plane, with increasingly better alignment progressing from phenyl to 1-naphthalene to 9-anthracene.
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In this paper, we present the case for molecular-recognition approaches for sulfate removal from radioactive wastes via the use of anion-sequestering systems selective for sulfate, using either liquid-liquid extraction or crystallization. Potential benefits of removing sulfate from the waste include improved vitrification of the waste, reduced waste-form volume, and higher waste-form performance, all of which lead to potential cleanup schedule acceleration and cost savings. The need for sulfate removal from radioactive waste, especially legacy tank wastes stored at the Hanford site, is reviewed in detail and primarily relates to the low solubility of sulfate in borosilicate glass. Traditional methods applicable to the separation of sulfate from radioactive wastes are also reviewed, with the finding that currently no technology has been identified and successfully demonstrated to meet this need. Fundamental research in the authors' laboratories targeting sulfate as an important representative of the class of oxoanions is based on the hypothesis that designed receptors may provide the needed ability to recognize sulfate under highly competitive conditions, in particular where the nitrate anion concentration is high. Receptors that have been shown to have promising affinity for sulfate, either in extraction or in crystallization experiments, include hexaurea tripods, tetraamide macrocycles, cyclo[8]pyrroles, calixpyrroles, and self-assembled urea-lined cages. Good sulfate selectivity observed in the laboratory provides experimental support for the proposed molecular-recognition approach.
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SNS platinum(II) pincer complexes reversibly bind and release the surrogate half sulfur mustard, 2-chloroethyl ethyl sulfide (CEES). The switch-like behavior of the pincers is attributed to a reversible transformation between the thioamide and iminothiolate forms of the pincer skeleton under slightly acidic and basic conditions, respectively. An amide-based palladium(II) pincer complex also binds CEES, as confirmed crystallographically and by NMR.
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Binding and structural aspects of anions with tetraamido/diquaternized diamino macrocyclic receptors containing m-xylyl, pyridine, and thiophene spacers are reported. (1)H NMR studies indicate that the quaternized receptors display higher affinities for anions compared to corresponding neutral macrocycles. The macrocycles containing pyridine spacers consistently display higher affinity for a given anion compared to those with either m-xylyl or thiophene spacers. The m-xylyl- and pyridine-containing receptors exhibit high selectivity for H(2)PO(4)(-) in DMSO-d(6) with association constants, K(a) = 1.09 × 10(4) and >10(5) M(-1), respectively, and moderate selectivity for Cl(-) with K(a) = 1.70 × 10(3) and 5.62 × 10(4) M(-1), respectively. Crystallographic studies for the Cl(-) and HSO(4)(-) complexes indicate that the m-xylyl-containing ligand is relatively elliptical in shape, with the two charges at ends of the major axis of the ellipse. The anions are hydrogen bonded with the macrocycle but are outside the ligand cavity. In the solid state, an unusual low-barrier hydrogen bond (LBHB) was discovered between two of the macrocycle's carbonyl oxygen atoms in the HSO(4)(-) complex. The pyridine-containing macrocycle folds so that the two pyridine units are face-to-face. The two I(-) ions are chelated to the two amides adjacent to a given pyridine. In the structure of the thiophene containing macrocycle with two BPh(4)(-) counterions, virtually no interaction was observed crystallographically between the macrocycle and the bulky anions.
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Amidas/química , Compuestos Macrocíclicos/química , Aminas/química , Cloruros/química , Cristalografía por Rayos X , Enlace de Hidrógeno , Compuestos Macrocíclicos/síntesis química , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Conformación MolecularRESUMEN
Mustard gas, bis(ß-chloroethyl) sulfide (HD), is highly toxic and harmful to humans and the environment. It comprises one class of chemical warfare agents (CWAs) that was used in both World Wars I and II. The three basic analogues or surrogates are: the monochloro derivative, known as the half mustard, 2-chloroethyl ethyl sulfide (CEES); an oxygen analogue, bis(ß-chloroethyl) ether (BCEE); and several nitrogen analogues based on the 2,2'-dichlorodiethylamine framework (e.g., HN1, HN2, and HN3). The origin of their toxicity is considered to be from the formation of three-membered heterocyclic ions, a reaction that is especially accelerated in aqueous solution. The reaction of these cyclic ion intermediates with a number of important biological species such as DNA, RNA and proteins causes cell toxicity and is responsible for the deleterious effects of the mustards. While a number of studies have been performed over the last century to determine the chemistry of these compounds, early studies suffered from a lack of more sophisticated NMR and X-ray techniques. It is now well-established that the sulfur and nitrogen mustards are highly reactive in water, while the oxygen analog is much more stable. In this study, we review and summarize results from previous studies, and add results of our own studies of the reactivity of these mustards toward various nonaqueous solvents and nucleophiles. In this manner a more comprehensive evaluation of the stability and reactivity of these related mustard compounds is achieved.
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Sustancias para la Guerra Química/química , Gas Mostaza/química , Compuestos de Mostaza Nitrogenada/química , Compuestos de Oxígeno/química , Animales , Cristalografía por Rayos X , Humanos , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Solventes/química , Solventes/clasificaciónRESUMEN
The design of supramolecular hosts for anions began with simple diaza bicycles, named katapinands, and has evolved over the last 40 years to a number of elegantly designed receptors capable of binding many different anions. About the same time the term cryptand appeared in reference to another bicyclic compound that was selective for alkaline-earth ions. Since the first report these simple bicycles, a vast arena of hosts has appeared, including acyclic, monocyclic, and other multicyclic supramolecular receptors. Studies of these systems have revealed considerable information about anion coordination chemistry, including the fact that many of these complexes mimic their transition-metal corollaries in terms of coordination numbers. However, for anions interactions occur via H-bonding most often, rather than the coordinate covalent or dative bonds observed in transition-metal coordination. This critical review examines the design of enclosed, primarily bicyclic cryptands as hosts for anions, with a small scattering of higher polyhedra when deemed appropriate to the discussion. In order to show the development (evolution) of the field, key examples of early work will be noted and compared with more recent developments (136 references).
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Supramolecular insight to intra- and inter-ionic interactions in two inositol hexaphosphate conformers as a function of pH was enabled by NMR and crystallographic studies. These findings also shed light on the complex interactive roles of extended salt-water arrays through the crystal "solution" lattice.
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Solid-state and solution studies were performed to determine if F(-) is encapsulated by anion hosts in both media. X-ray crystal structure determinations were compared with both (1)H and (19)F solution NMR data. Three hosts were studied: (1) two polyamide hosts, one with isophthaloyl spacers and the other with pyridine spacers, and (2) a polythioamide host with pyridine spacers. Binding studies showed that the pyridine-containing amide cryptand shows the highest affinity (K(a) > 10(5) in DMSO-d(6)), with the other hosts at least a factor of 10 lower. All of the cryptands appear to encapsulate F(-) in solution, where a deuterium-exchange reaction with DMSO-d(6) can be monitored by (19)F NMR. Four crystal structures are reported and compared: two for the pyridine-containing free base hosts and two for encapsulated F(-) complexes of the two amide-based cryptands.
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A tricyclic host for anions consisting of two tetraamide monocycles attached by two ethylene chains was designed and synthesized. Structural and binding results indicate that the receptor is selective for linear triatomic anions. Crystallographic data for two hydrated free bases, along with FHF(-), N(3)(-), and SO(4)(2-) complexes indicate that there are at least two preferred gross conformations for the host, one of which possesses pseudo-D(2) symmetry and the other pseudo-C(2h) symmetry. Both FHF(-) and N(3)(-) are encapsulated in the pseudo-D(2) symmetric complex, bridging the two tetraamido macrocyclic halves. The pseudo-C(2h) octahydrate structure shows an ice-like H-bonded (H(2)O)(6) array of water molecules embedded in the host cavity. The SO(4)(2-) structure has a nearly superimposable host conformation to the octahydrate but with the SO(4)(2-) anions lying outside the host. Binding studies in DMSO-d(6) indicate selectivity for FHF(-), with lesser affinity for other inorganic anions.
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Structurally elusive inositol hexakisphosphates have been trapped in host-guest sandwiches between two picolinamide macrocycles that remain intact in solution, aided by hydrogen bonds and electrostatic interactions. This first report of macrocyclic complexes of inositol hexakisphosphates provides structural insight to significant biosources of phosphorus that impact the global phosphorus cycle.
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In this communication, a new approach to enhancing the efficacy of liquid-liquid anion exchange is demonstrated. It involves the concurrent use of appropriately chosen hydrogen-bond-donating (HBD) anion receptors in combination with a traditional quaternary ammonium extractant. The fluorinated calixpyrroles 1 and 2 and the tetraamide macrocycle 4 were found to be particularly effective receptors. Specifically, their use allowed the extraction of sulfate by tricaprylmethylammonium nitrate to be effected in the presence of excess nitrate. As such, the present work provides a rare demonstration of overcoming the Hofmeister bias in a competitive environment and the first to the authors' knowledge wherein this difficult-to-achieve objective is attained using a neutral HBD-based anion binding agent under conditions of solvent extraction.
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Calixarenos/química , Lactamas Macrocíclicas/química , Porfirinas/química , Sulfatos/aislamiento & purificación , Amidas/química , Técnicas de Química Analítica/métodos , Intercambio Iónico , Sulfatos/químicaRESUMEN
Neutral and charged multitopic cyclophane-capped anion hosts connected by three or four diamide/monoamine chains and a decomposition product with two chains have been synthesized and characterized. The chains in the two former hosts fold together to form one or two binding pockets, respectively, and FHF(-) and several phosphate complexes have been obtained with the anions nestled in these pockets. The decomposition product also shows propensity for binding dicarboxylates, as evidenced by an isophthalate crystal structure.