Aromatic Donor-acceptor Interactions Research Articles

Cover Feature: Organocatalytic Assembly Based on Aromatic Donor–Acceptor Interactions for the Asymmetric Aldol Reaction on Water (ChemCatChem 11/2023)

The Cover Feature shows that aromatic donor modified prolinamide (red robot) and aromatic acceptor modified thiourea (blue robot) are brought in close proximity to each other by the aromatic donor-acceptor interaction, so they can work cooperatively to catalyze asymmetric aldol reactions. In their Research Article, J. Liang, Y. Liu and co-workers reported the first organocatalytic system self-assembled through the aromatic donor-acceptor interaction. More intriguing is, under the biphasic on-water condition as exhibited in this picture, this catalytic assembly showed the high catalytic activity and stereoselectivity for a broad substrate scope. More information can be found in the Research Article by J. Liang, Y. Liu and co-workers.

Organocatalytic Assembly Based on Aromatic Donor–Acceptor Interactions for the Asymmetric Aldol Reaction on Water

AbstractAromatic donor modified prolinamide and aromatic acceptor modified thiourea were synthesized. They self‐assembled into a cooperative organocatalytic system through the aromatic donor‐acceptor interaction and catalyzed aldol reactions in high yields and stereoselectivity on water. The aromatic donor‐acceptor interaction was confirmed by mass spectrum, UV‐vis titraition and 1H‐NMR titration experiments.

A Cheminformatics Study Regarding the Human Health Risks Assessment of the Stereoisomers of Difenoconazole.

Difenoconazole is a chemical entity containing two chiral centers and having four stereoisomers: (2R,4R)-, (2R,4S)-, (2S,4R)- and (2S,4S)-difenoconazole, the marketed product containing a mixture of these isomers. Residues of difenoconazole have been identified in many agricultural products and drinking water. A computational approach has been used to evaluate the toxicological effects of the difenoconazole stereoisomers on humans. It integrates predictions of absorption, distribution, metabolism, excretion and toxicity (ADMET) profiles, prediction of metabolism sites, and assessment of the interactions of the difenoconazole stereoisomers with human cytochromes, nuclear receptors and plasma proteins by molecular docking. Several toxicological effects have been identified for all the difenoconazole stereoisomers: high plasma protein binding, inhibition of cytochromes, possible hepatotoxicity, neurotoxicity, mutagenicity, skin sensitization potential, moderate potential to produce endocrine disrupting effects. There were small differences in the predicted probabilities of producing various biological effects between the distinct stereoisomers of difenoconazole. Furthermore, there were significant differences between the interacting energies of the difenoconazole stereoisomers with plasma proteins and human cytochromes, the spectra of the hydrogen bonds and aromatic donor–acceptor interactions being quite distinct. Some distinguishing results have been obtained for the (2S,4S)-difenoconazole: it registered the highest value for clearance, exposed reasonable probabilities to produce cardiotoxicity and carcinogenicity and negatively affected numerous nuclear receptors.

Polyimide-supported Cu/2,2,6,6-tetramethyl-1-piperidine-N-oxyl catalytic systems: Aromatic donor-acceptor interaction-directed cooperative catalysis

Non-covalent immobilization of multifunctional catalysts onto polymer supports is a promising technique to build highly efficient heterogeneous cooperative catalysts. Here, we present a strategy to build polyimide-supported Cu/2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) catalytic systems based on hydrophobic interactions and aromatic donor-acceptor interactions. Pyrene-containing catalytic species and naphthalene diimide (NDI)-based polyimides were chosen for the preparation of nanoparticle catalysts using the nanoprecipitation technique. The cooperative behaviors of catalytic components were evaluated by the catalytic activities of aerobic oxidation of benzyl alcohol (BnOH) in water. We studied the influence of effective constituent ratio of polymers, chain length of monomer, and the incorporation of a second monomer on catalytic activities. The aggregate structures were investigated by X-ray powder diffraction (XRD) patterns and small angle X-ray scattering (SAXS), and speculated to be random distributions of aromatic stacking clusters within nanoparticle catalysts. This strategy will find applications in the construction of other multifunctional heterogeneous catalysts.

Effect of hydrogen bonds and π⋯π interactions on the crystallization of phenyl-perfluorophenyl amides: understanding the self-organization of a cocrystal

Crystallization mechanisms were proposed to investigate hydrogen bond and aromatic donor–acceptor interactions in a series of phenyl–perfluorophenyl amides. The modulation of NH⋯OC bonds and aryl complementarity drove a new cocrystal growth.

Tryptophan association in water driven by charge-transfer interactions with electron-deficient aromatic haptens.

The ability of a series of electron-deficient aromatic compounds to form charge-transfer complexes with tryptophan in water has been evaluated by X-ray diffraction studies, UV-vis spectra and NMR. As dinitrophenyl (DNP) ligands are well-known to generate antibody-mediated responses and the π-π stacking interactions with tryptophan residues of the antibody Fab fragment have been reported, most of the aromatic receptors studied here are nitro derivatives. Charge-transfer interactions between the rich indole ring of tryptophan and the electron-deficient aromatic receptors have been observed in the solid state, as four crystal structures of the complexes were obtained. The aromatic donor-acceptor interactions in solution were also verified by UV-vis and NMR spectroscopy. The association of the tripeptide Trp-Gly-Trp, a motif found in antigen Ag43, with the electron-deficient aromatic diimide was also studied by UV-vis and NMR spectroscopy. Our results show that these simple electron-deficient molecules could potentially behave as novel haptens and be incorporated in more elaborated drugs targeting protein-protein interactions, due to the synergistic effect of multiple non-covalent interactions.

Poly(dimethylsiloxane) and oligo(dimethylsiloxane) solvent effects on aromatic donor-acceptor interactions.

Solvents with a wide range of polarities, including poly(dimethylsiloxane) and oligo(dimethylsiloxane), were used to evaluate aromatic donor-acceptor interactions between pyrene and pyromellitic diimide derivatives. The donor-acceptor interactions were stronger in siloxane solvents than in aliphatic solvents, possibly because of the poor solubility of the aromatics in siloxanes.

Aromatic Donor-Acceptor Interaction-Based Co(III)-salen Self-Assemblies and Their Applications in Asymmetric Ring Opening of Epoxides.

Aromatic donor-acceptor interaction as the driving force to assemble cooperative catalysts is described. Pyrene/naphthalenediimide functionalized Co(III)-salen complexes self-assembled into bimetallic catalysts through aromatic donor-acceptor interactions and showed high catalytic activity and selectivity in the asymmetric ring opening of various epoxides. Control experiments, nuclear magnetic resonance (NMR) spectroscopy titrations, mass spectrometry measurement, and X-ray crystal structure analysis confirmed that the catalysts assembled based on the aromatic donor-acceptor interaction, which can be a valuable noncovalent interaction in supramolecular catalyst development.

Synthesis, crystal structure, vibrational study, optical properties and Hirshfeld surface analysis of bis(2,6-diaminopyridinium) tetrachloridocobaltate(II) monohydrate

The title organic–inorganic hybrid compound, (C5H8N3)2 [CoCl4]·H2O, was synthesized by slow evaporation at room temperature. Single-crystal X-ray diffraction analysis indicates that the asymmetric unit in this compound consists of one tetrahedral geometry [CoCl4]2-, two protonated organic cations (C5H8N3)+ and one water molecule of crystallization, all of which lie in general positions. In the crystal structure, the inorganic layers are built from tetrachloridocobaltate anions [CoCl4]2- and free water molecules, linked together by OH⋯Cl hydrogen bonds. The organic cations are intercalated between the inorganic layers via NH⋯Cl hydrogen bonds and form chains through aromatic donor–acceptor interactions. Crystal cohesion is achieved through NH⋯Cl, OH⋯Cl, NH⋯O and CH⋯Cl hydrogen bonds between organic cations, inorganic anions and the water molecules building up a three-dimensional network. The functional groups present in the crystal were studied by FTIR spectroscopy. Investigation of the optical properties of the compound confirmed its semiconducting properties by revealing a direct optical band gap at 1.67 eV. Photoluminescence proprieties were also reported. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) reveal that the structure is dominated by H⋯Cl/Cl⋯H and H⋯H contacts.

Raising the Bar in Aromatic Donor-Acceptor Interactions with Cyclic Trinuclear Gold(I) Complexes as Strong π-Donors.

Aromatic donor-acceptor interactions are of high importance in supramolecular chemistry, materials science and biology. Compared to other noncovalent interactions, such as hydrogen bonding, the binding is often weak. Here we show that strong donor-acceptor interactions between planar aromatics with binding free energies down to -10.1 kcal mol-1 and association constants of up to 2.34 × 107 L mol-1 for 1:1 complexes can be realized using cyclic trinuclear complexes of gold(I) with pyridinate, imidazolate, or carbeniate ligands. Data were obtained through NMR and UV/vis absorption spectroscopic studies and supported by quantum chemical calculations for a variety of acceptors. By using a specifically designed bridged naphthalene diimide-based acceptor with only one binding site, we furthermore show that a 1:2 (donor:acceptor) binding model is best suited to quantify the donor and acceptor/complex equilibrium. Scanning electron microscopy on selected donor-acceptor pairs shows crystalline supramolecular assemblies. We anticipate this study to be relevant for the future design of supramolecular systems and chemical sensors and the determination of binding energies between planar donors and acceptors.

Neighboring Component Effect in a Tri-stable [2]Rotaxane

The redox properties of cyclobis(paraquat- p-phenylene)cyclophane (CBPQT4+) render it a uniquely variable source of recognition in the context of mechanically interlocked molecules, through aromatic donor-acceptor interactions in its fully oxidized state (CPBQT4+) and radical-pairing interactions in its partially reduced state (CBPQT2(•+)). Although it is expected that the fully reduced neutral state (CBPQT(0)) might behave as a π-donating recognition unit, resulting in a dramatic change in its binding properties when compared with the other two redox states, its role in rotaxanes has not yet been investigated. To address this challenge, we report herein the synthesis of a tri-stable [2]rotaxane in which a CBPQT4+ ring is mechanically interlocked with a dumbbell component containing five recognition sites-(i) a bipyridinium radical cation (BIPY(•+)) located centrally along the axis of the dumbbell, straddled by (ii) two tetrafluorophenylene units linked to (iii) two triazole rings. In addition to the selective recognition between (iv) the CBPQT4+ ring and the triazole units, and (v) the CBPQT2(•+) ring and the reduced BIPY(•+) unit in the dumbbell component, investigations in solution have now confirmed the presence of additional non-covalent bonding interactions between the CBPQT(0) ring, acting as a donor in its neutral state, and the two tetrafluorophenylene acceptors in the dumbbell component. The unveiling of this piece of molecular recognition in a [2]rotaxane is reminiscent of the existence in much simpler, covalently linked, organic molecules of neighboring group participation (anchimeric assistance giving way to transannular interactions) in small-, medium-, and large-membered rings.

Phthalocyanine photosensitizer in polyethylene glycol-block-poly(lactide-co-benzyl glycidyl ether) nanocarriers: Probing the contribution of aromatic donor-acceptor interactions in polymeric nanospheres

For best photosensitizer activity phthalocyanine dyes used in photodynamic therapy should be molecularly dispersed. Polyethylene glycol-block-polylactide derivatives presenting benzyl side-groups were synthesized to encapsulate a highly lipophilic phthalocyanine dye (AlClPc) and evaluate the effect of π-π interactions on the nanocarrier colloidal stability and dye dispersion. Copolymers with 0, 1, 2 and 6 mol% of benzyl glycidyl ether (BGE) were obtained via polyethylene glycol initiated ring-opening copolymerization of D,l-lactide with BGE. The block copolymers formed stable, monodisperse nanospheres with low in vitro cytotoxicity. AlClPc loading increased the nanosphere size and affected their colloidal stability. The photo-physical properties of the encapsulated dye, studied in batch and after separation by field flow fractionation, demonstrated the superiority of plain PEG-PLA over BGE-containing copolymers in maintaining the dye in its monomeric (non-aggregated) form in aqueous suspension. High dye encapsulation and sustained dye release suggest that these nanocarriers are good candidates for photodynamic therapy.

High-Yielding Synthesis of Chiral Donor–Acceptor Catenanes

We report the synthesis of [2]catenanes (Hopf links) in water utilizing disulfides and aromatic donor-acceptor interactions. The electron-rich dialkoxynaphthalene (DN) building blocks interact with electron-deficient naphthalenediimide (NDI) moieties connected by a polyamine chain. We study the effect of the polyamine linkers on the behavior of the library. The polyamine's length and the number of nitrogen atoms in the chain affect the library distribution, leading in some cases to the assembly of catenanes in up to 93% yield.

Redox Control of the Binding Modes of an Organic Receptor.

The modulation of noncovalent bonding interactions by redox processes is a central theme in the fundamental understanding of biological systems as well as being ripe for exploitation in supramolecular science. In the context of host-guest systems, we demonstrate in this article how the formation of inclusion complexes can be controlled by manipulating the redox potential of a cyclophane. The four-electron reduction of cyclobis(paraquat-p-phenylene) to its neutral form results in altering its binding properties while heralding a significant change in its stereoelectronic behavior. Quantum mechanics calculations provide the energetics for the formation of the inclusion complexes between the cyclophane in its various redox states with a variety of guest molecules, ranging from electron-poor to electron-rich. The electron-donating properties displayed by the cyclophane were investigated by probing the interaction of this host with electron-poor guests, and the formation of inclusion complexes was confirmed by single-crystal X-ray diffraction analysis. The dramatic change in the binding mode depending on the redox state of the cyclophane leads to (i) aromatic donor-acceptor interactions in its fully oxidized form and (ii) van der Waals interactions when the cyclophane is fully reduced. These findings lay the foundation for the potential use of this class of cyclophane in various arenas, all the way from molecular electronics to catalysis, by virtue of its electronic properties. The extension of the concept presented herein into the realm of mechanically interlocked molecules will lead to the investigation of novel structures with redox control being expressed over the relative geometries of their components.

Aromatic donor-acceptor interactions in non-polar environments.

We have evaluated the strength of aromatic donor-acceptor interactions between dialkyl naphthalenediimide and dialkoxynaphthalene in non-polar environments. (1)H NMR, UV-vis spectroscopy and isothermal titration calorimetry were used to characterise this interaction. We concluded that the strength of donor-acceptor interactions in heptane is sufficient to drive supramolecular assemblies in this and other aliphatic solvents.

ChemInform Abstract: Progress in the Synthesis and Exploitation of Catenanes Since the Millennium

AbstractReview: 131 refs.

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

Bis(pyrene)metal complexes of vanadium, niobium and titanium: isolable homoleptic pyrene complexes of transition metals.

Reduction of VCl3(THF)3 (THF is tetrahydrofuran) and NbCl4(THF)2 by alkali metal pyrene radical anion salts in THF affords the paramagnetic sandwich complexes bis[(1,2,3,3a,10a,10b-η)-pyrene]vanadium(0), [V(C16H10)2], and bis[(1,2,3,3a,10a,10b-η)-pyrene]niobium(0), [Nb(C16H10)2]. Treatment of tris(naphthalene)titanate(2-) with pyrene provides the isoelectronic titanium species, isolated as an (18-crown-6)potassium salt, namely catena-poly[[(18-crown-6)potassium]-μ-[(1,2-η:1,2,3,3a,10a,10b-η)-pyrene]-titanate(-I)-μ-[(1,2,3,3a,10a,10b-η:6,7-η)-pyrene]], {[K(C12H24O6)][Ti(C16H10)2]}n. The first two compounds have very similar packing, with neighboring molecules arranged orthogonally to one another, such that aromatic donor-acceptor interactions are likely responsible for the specific arrangement. The asymmetric unit contains a half-occupancy metal center η(6)-coordinated to one pyrene ligand, with the full M(pyrene)2 molecule generated by a crystallographic inversion center. In the titanium compound, the cations and anions are in alternating contact throughout the crystal structure, in one-dimensional chains along the [101] direction. As in the other two compounds, the asymmetric unit contains a half-occupancy Ti atom η(6)-coordinated to one pyrene ligand. Additionally, the asymmetric unit contains one half of an (18-crown-6)potassium cation, located on a crystallographic inversion center coincident with the K atom. The full formula units are generated by those inversion centers. In all three structures, the pyrene ligands are eclipsed and sandwich the metals in one of two inversion-related sites. These species are of interest as the first isolable homoleptic pyrene transition metal complexes to be described in the scientific literature.

Progress in the synthesis and exploitation of catenanes since the Millennium

Catenanes - molecules consisting of interlocked macrocyclic rings - have been prepared by templation strategies for some thirty years. The utilization of Cu(I) cation, aromatic donor-acceptor interactions and hydrogen bonding assisted self-assembly strategies has led to the construction of numerous examples of these aesthetically pleasing species. This review seeks to discuss key developments in the synthesis and functional application of catenanes that have occurred since the Millennium. The much expanded range of metal cation templates; the genesis and growth of anion templation, as well as the use of alternative supramolecular interactions (halogen bonding and radical templation) and thermodynamically controlled reactions to synthesize catenanes are detailed. The class of catenanes that may be described as "molecular machines" are then highlighted and to conclude, attempts to fabricate catenanes onto surfaces and into metal organic frameworks (MOFs) are discussed.

Disulfide exchange: exposing supramolecular reactivity through dynamic covalent chemistry

A Tutorial Review of the subtle supramolecular interactions influencing the outcomes of equilibrating systems, focusing on the dynamic covalent chemistry (DCC) of disulfide exchange reactions, is presented. We discuss the topics of cation-π interactions (2.1), hydrophobic effects (2.2), hydrogen bonding interactions (2.3) aromatic donor-acceptor interactions (2.4), and metal-ligand interactions (2.5) in the context of dynamic disulfide chemistry.