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A novel isopthalamide based receptor H 2 L2 featuring two p-benzoic acid units has been synthesised and its anion binding properties analysed by 1 H-NMR spectroscopy in DMSO-d 6 /0.5 % H 2 O. As expected, in the presence of tetrabutylammonium (TBA) fluoride the deprotonation of the carboxylic acid moieties was observed. However, the deprotonated receptor L2 2- was able to bind the in situ formed HF 2 - via the formation of H-bonds with the amide NHs. When H 2 L2 was dissolved in THF and 4 equivalents of TBAF were added in CH 3 CN a unique sol-gel transition occurred giving rise to a stable thixotropic supramolecular gel. Theoretical calculations elucidated the gelation mechanism and strongly support the findings observed experimentally., (© 2025 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

We designed a new cyanine dye 1, with two pedant rod-like groups, capable of forming two distinct two-dimensional (2D) supramolecular polymorphs in methylcyclohexane; an H-type aggregate (Agg-H 2 ) and a J-type aggregate (Agg-J). Importantly, these two polymorphs were not accessed through polymerization events, and instead through the thermal transformation of a third particle-like polymorph (Agg-H 1 ) formed by the anti-cooperative assembly of 1. While Agg-H 2 is generated upon cooling the solution of Agg-H 1 by a thermoreversible polymorph transition, the Agg-J was obtained through a hidden pathway by combining sonication and cooling to the Agg-H 1 solution. This is the first report on the obtention of H- and J-type cyanine polymorphs that in turn could be isolated in solid-state to render two new 2D photoactive materials. This paper unveils new strategies for designing 2D supramolecular polymers using calamitic residues, but also undercovers relevant aspects of pathway complexity and polymorph transitions that might be crucial for developing novel photonic systems., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The Protein Data Bank (PDB) was scrutinized for the presence of noncovalent O ⋅ ⋅ ⋅ Al Triel Bonding (TrB) interactions, involving protein residues (e. g. GLU and GLN), adenosine/guanine diphosphate moieties (ADP and GDP), water molecules and two aluminum fluorides (AlF 3 and AlF 4 - ). The results were statistically analyzed, revealing a vast number of O ⋅ ⋅ ⋅ Al contacts in the active sites of phosphoryl transfer enzymes, with a marked directionality towards the Al σ-/π-hole. The physical nature of the TrBs studied herein was analyzed using Molecular Electrostatic Potential (MEP) maps, the Quantum Theory of Atoms in Molecules (QTAIM), the Non Covalent Interaction plot (NCIplot) visual index and Natural Bonding Orbital (NBO) studies. As far as our knowledge extends, it is the first time that O ⋅ ⋅ ⋅ Al TrBs are analyzed within a biological context, participating in protein trapping mechanisms related to phosphoryl transfer enzymes. Moreover, since they are involved in the stabilization of aluminum fluorides inside the protein's active site, we believe the results reported herein will be valuable for those scientists working in supramolecular chemistry, catalysis and rational drug design., (© 2024 The Author(s). ChemPlusChem published by Wiley-VCH GmbH.)

The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a σ-hole interaction that is essentially absent in biocatalysis. For this purpose, stibine catalysts were equipped with a biotin derivative and combined with streptavidin mutants to identify an efficient transfer hydrogenation catalyst for the reduction of a fluorogenic quinoline substrate. Increased catalytic activity from wild-type streptavidin to the best mutants coincides with the depth of the σ hole on the Sb(V) center, and the emergence of saturation kinetic behavior. Michaelis-Menten analysis reveals transition-state recognition in the low micromolar range, more than three orders of magnitude stronger than the millimolar substrate recognition. Carboxylates preferred by the best mutants contribute to transition-state recognition by hydrogen-bonded ion pairing and anion-π interactions with the emerging pyridinium product. The emergence of challenging stereoselectivity in aqueous systems further emphasizes compatibility of pnictogen bonding with higher order systems catalysis., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The -N + (CH 3 ) 3 residue is present in acetylcholine (ACh) and in many of its analogues which are used as selective ACh agonist or antagonists for human therapy. The X-ray structures of four ACh derivatives show the presence of short and linear contacts between the C atoms of -N + (CH 3 ) 3 groups and lone pair possessing atoms. These contacts can be rationalized as tetrel bonds (TtBs) thanks to their geometric features. Interrogation of the Protein Data Bank suggests that similar -N + -C⋅⋅⋅nucleophile contacts affect the details of the binding of ACh and its derivatives to proteins. Quantum theory of atoms in molecules, noncovalent interaction plot, and natural bond orbital analyses consistently confirm that the -N + -C⋅⋅⋅nucleophile contacts observed in small molecule crystals and in substrate/protein complexes are attractive in nature and can be rationalized as TtBs. TtBs involving methyl groups of the -N + (CH 3 ) 3 moiety can be proposed as a new item in the palette of interactions allowing the compounds containing this pharmacophoric unit to bind to their target protein and/or to express their biological/pharmacological properties., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

A microwave-assisted synthesis of 7-amino-1,2,4-triazolo[1,5-a][1,3,5]triazine-2-propanamides was developed using a three-component, catalyst-free reaction of cyanamide and trimethyl orthoformate with 3-(5-amino-1H-1,2,4-triazol-3-yl)propanamides (3). The reaction tolerated structurally diverse substrates and proceeded chemo- and regio-selectively, affording the target compounds in high purity in 5-10 minutes. The convenient chromatography-free isolation and purification of the products add practicality to this method. The structural features of the prepared compounds were investigated using dynamic NMR spectroscopy, X-ray crystallography and computational chemistry calculations. X-ray crystallography performed on a representative compound, 3-(7-amino-1,2,4-triazolo[1,5-a][1,3,5]triazin-2-yl)-N-(4-benzyl)propanamide (4 l), showed the overall molecular conformation to adopt the shape of the letter C. Notable localisation of π-electron density is found within the 1,2,4-triazolo[1,5-a][1,3,5]triazine system; a relatively short C-NH 2 bond is consistent with restricted rotation about this bond. This study also presents a detailed analysis of the molecular interactions in 4 l using DFT and QTAIM methods with a focus on the hydrogen-bonding and π-stacking interactions that influence the molecular packing of 4 l. The findings reveal the significant roles of N-H⋅O, N-H⋅N and C-H⋅N interactions, along with electrostatically enhanced π⋅π contacts. A broad screening for insecticidal, fungicidal and herbicidal properties identified several compounds with potent herbicidal activity against Matricaria inodora., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Herein we have evidenced the formation of favorable π-hole Br⋅⋅⋅metal noncovalent interactions (NCIs) involving elements from groups 9, 11 and 12. More in detail, M (M=Co 2+ , Ni 2+ , Cu 2+ and Zn 2+ ) containing porphyrins have been synthesized and their supramolecular assemblies structurally characterized by means of single crystal X-ray diffraction and Hirshfeld surface analyses, revealing the formation of directional Br⋅⋅⋅M contacts in addition to ancillary hydrogen bond and lone pair-π bonds. Computations at the PBE0-D3/def2-TZVP level of theory revealed the π-hole nature of the Br⋅⋅⋅M interaction. In addition, the physical nature of these NCIs was studied using Quantum Chemistry methodologies, providing evidence of π-hole Spodium and Regium bonds in Zn 2+ and Cu 2+ porphyrins, in addition to unveiling the presence of a π-hole for group 9 (Co 2+ ). On the other hand, group 10 (Ni 2+ ) acted as both electron donor and acceptor moiety without showing an electropositive π-hole. Owing to the underexplored potential of π-hole interactions in transition metal chemistry, we believe the results reported herein will be useful in supramolecular chemistry, organometallics, and solid-state chemistry by i) putting under the spotlight the π-hole chemistry involving first row transition metals and ii) unlocking a new tool to direct the self-assembly of metalloporphyrins., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In X-ray structures of the isomorphic mer-[IrX 3 (THT)(CNXyl) 2 ] (X=Cl 1, Br 2; THT=tetrahydrothiophene; Xyl=2,6-Me 2 C 6 H 3 -) complexes, we revealed short intermolecular contacts between the C-atom of an isocyanide methyl group and halide ligands of another molecule. Geometrical consideration of the X-ray data and analysis of appropriate DFT studies allowed the attribution of these contacts to C Me ⋅⋅⋅X-Ir III (X=Cl, Br) tetrel bond. Specifically, through the application of DFT calculations and various theoretical models, the presence of tetrel bonding interactions was validated, and the contribution of the C Me ⋅⋅⋅X-Ir III interaction was assessed. The reinforcement of the tetrel bond upon the isocyanide coordination to iridium(III) is substantiated by molecular electrostatic potential (MEP) surface calculations. To distinguish the tetrel bonding characteristics of CMe⋅⋅⋅X-Ir III (X=Cl, Br) interactions from conventional hydrogen bonding, we employed multiple computational methodologies, including Natural Bond Orbital (NBO) analysis and Electron Localization Function (ELF) analysis. Additionally, Energy Decomposition Analysis (EDA) was applied to selected model systems to explore the underlying physical nature of these interactions., (© 2024 Wiley-VCH GmbH.)

The chemistry of light dipnictenes has been widely investigated in the last century with remarkable achievements especially for azobenzene derivatives. In contrast, distibenes and dibismuthenes are relatively rare and show very limited reactivity. Herein, we have designed a protocol using visible light to enhance the reactivity of heavy dipnictenes. Exploiting the distinctive π-π* transition, we have been able to isolate unique examples of dipnictene-cobalt complexes. The reactivity of the distibene complex was further exploited using red light in the presence of a diazoolefin to access an unusual four-membered bicyclo[1.1.0]butane analog, containing only a single carbon atom. These findings set the bases to a conceptually new strategy in heavy element double bonds chemistry where visible light is at the front seat of bond activation., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

It is well-known that people suffering from hyperglycemia have a higher propensity to develop Parkinson's disease (PD). One of the most plausible mechanisms linking these two pathologies is the glycation of neuronal proteins and the pathological consequences of it. α-Synuclein, a key component in PD, can be glycated at its fifteen lysine. In fact, the end products of this process have been detected on aggregated α-synuclein isolated from in vivo. However, the consequences of glycation are not entirely clear, which are of crucial importance to understand the mechanism underlying the connection between diabetes and PD. To better clarify this, we have here examined how methylglyoxal (the most important carbonyl compound found in the cytoplasm) affects the conformation and aggregation propensity of α-synuclein, as well as its ability to cluster and fuse synaptic-like vesicles. The obtained data prove that methylglyoxal induces the Lys-Lys crosslinking through the formation of MOLD. However, this does not have a remarkable effect on the averaged conformational ensemble of α-synuclein, although it completely depletes its native propensity to form soluble oligomers and insoluble amyloid fibrils. Moreover, methylglyoxal has a disrupting effect on the ability of α-synuclein to bind, cluster and fusion synaptic-like vesicles., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The dynamic nature of calamitic liquid crystals is exploited to perform isothermal phase transitions driven by dynamic covalent chemistry. For this purpose, nematic (N) arrays based on aldehyde 1 were treated with different amines (A-E) in an on-surface process, which resulted in different isothermal phase transitions. These phase transformations were caused by in situ imination reactions and are dependent on the nature of the added amine. Transitions from the N to crystal (1A, 1E), isotropic (1B), and smectic (Sm) (1C, 1D) phases were achieved, while the resulting materials feature thermotropic liquid crystal behavior. A sequential transformation from the N 1 to the Sm 1C and then to the N 1B was achieved by coupling an imination to a transimination processes and adjusting the temperature. All of these processes were well characterized by microscopic, spectroscopic, and X-ray techniques, unlocking not only the constitutional but also the structural aspects of the phase transitions. This work provides new insights into designing constitutionally and structurally adaptable liquid crystal systems, paving the way toward the conception of programable evolutive pathways and adaptive materials., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In this manuscript we evaluate the X-ray structure of five new pertechnetate derivatives of general formula [M(H 2 O) 4 (TcO 4 ) 2 ], M=Mg, Co, Ni, Cu, Zn (compounds 1-5) and one perrhenate compound Zn(H 2 O) 4 (ReO 4 ) 2 (6). In these complexes the metal center exhibits an octahedral coordination with the pertechnetate units as axial ligands. All compounds exhibit the formation of directional Tc⋅⋅⋅O Matere bonds (MaBs) that propagate the [M(H 2 O) 4 (TcO 4 ) 2 ], into 1D supramolecular polymers in the solid state. Such 1D polymers are linked, generating 2D layers, by combining additional MaBs and hydrogen bonds (HBs). Such concurrent motifs have been analyzed theoretically, suggesting the noncovalent σ-hole nature of the MaBs. The interaction energies range from weak (~ -2 kcal/mol) for the MaBs to strong (~ -30 kcal/mol) for the MaB+HB assemblies, where HB dominates. In case of M=Zn, the corresponding perrhenate Zn(H 2 O) 4 (ReO 4 ) 2 complex, has been also synthesized for comparison purposes, resulting in the formation of an isostructural X-ray structure, corroborating the structure-directing role of Matere bonds., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

As(III) S-adenosylmethionine methyltransferases, pivotal enzymes in arsenic metabolism, facilitate the methylation of arsenic up to three times. This process predominantly yields trivalent mono- and dimethylarsenite, with trimethylarsine forming in smaller amounts. While this enzyme acts as a detoxifier in microbial systems by altering As(III), in humans, it paradoxically generates more toxic and potentially carcinogenic methylated arsenic species. The strong affinity of As(III) for cysteine residues, forming As(III)-thiolate bonds, is exploited in medical treatments, notably in arsenic trioxide (Trisenox®), an FDA-approved drug for leukemia. The effectiveness of this drug is partly due to its interaction with cysteine residues, leading to the breakdown of key oncogenic fusion proteins. In this study, we extend the understanding of As(III)'s binding mechanisms, showing that, in addition to As(III)-S covalent bonds, noncovalent O⋅⋅⋅As pnictogen bonding plays a vital role. This interaction significantly contributes to the structural stability of the As(III) complexes. Our crystallographic analysis using the PDB database of As(III) S-adenosylmethionine methyltransferases, augmented by comprehensive theoretical studies including molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) analysis, emphasizes the critical role of pnictogen bonding in these systems. We also undertake a detailed evaluation of the energy characteristics of these pnictogen bonds using various theoretical models. To our knowledge, this is the first time pnictogen bonds in As(III) derivatives have been reported in biological systems, marking a significant advancement in our understanding of arsenic's molecular interactions., (© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

Kinases are enzymes that play a critical role in governing essential biological processes. Due to their pivotal involvement in cancer cell signaling, they have become key targets in the development of anti-cancer drugs. Among these drugs, those containing the 2,4-dihalophenyl moiety demonstrated significant potential. Here we show how this moiety, particularly the 2-fluoro-4-iodophenyl one, is crucial for the structural stability of the formed drug-enzyme complexes. Crystallographic analysis of reported kinase-inhibitor complex structures highlights the role of the halogen bonding that this moiety forms with specific residues of the kinase binding site. This interaction is not limited to FDA-approved MEK inhibitors, but it is also relevant for other kinase inhibitors, indicating its broad relevance in the design of this class of drugs., (© 2024 Wiley‐VCH GmbH.)

H-selenite anions (HSeO 3 - ) form in the solid unprecedented anionic supramolecular chains wherein single units are assembled via alternating short Se⋅⋅⋅O and H⋅⋅⋅O contacts. Crystallographic analyses and computational studies (the quantum theory of "atoms-in-molecules", QTAIM, and the noncovalent interaction plot, NCIPlot) consistently prove the attractive nature of these chalcogen bonds (ChBs) and hydrogen honds (HBs), the Janus-type character of HSeO 3 - anions which act as both donors and acceptors of ChB and HB, and the possible stability of anion dimers in solution. The effectiveness of the ChBs herein described may lead to consider the HSeO 3 - moiety as a new entry in the toolbox of crystal engineering based on ChB., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Homoleptic [L-I-L] + iodine(I) complexes (where L is a R 3 R 2 R 1 N tertiary amine) were synthesized via the [L-Ag-L] + → [L-I-L] + cation exchange reaction. In solution, the amines form [R 3 R 2 R 1 N-Ag-NR 1 R 2 R 3 ] + silver(I) complexes, which crystallize out from solution as the meso-[L-Ag-L] + complexes, as characterized by X-ray crystallography. The subsequent [L-I-L] + iodine(I) analogues were extremely reactive and could not be isolated in the solid state. Density functional theory (DFT) calculations were performed to study the Ag + -N and I + -N interaction energies in silver(I) and iodine(I) complexes, with the former ranging from -80 to -100 kJ mol -1 and latter from -260 to -279 kJ mol -1 . The X-ray crystal structures revealed Ag + ⋅⋅⋅C π and Ag + ⋅⋅⋅H-C short contacts between the silver(I) cation and flexible N-alkyl/N-aryl groups, which are the first of their kind in such precursor complexes., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl 3 or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Analyses of the Cambridge Structural Database and theoretical calculations (PBE0-D3/def2-TZVP level, atoms-in-molecules, natural bond orbital studies) prove the formation of net attractive noncovalent interactions between group 5 elements and electron-rich atoms (neutral or anionic). These kinds of bonding are markedly different from coordination bonds formed by the same elements and possess the distinctive features of σ-hole interactions. The term erythronium bond is proposed to denote these bonds. X-ray structures of vanadate-dependent bromoperoxidases show that these interactions are present also in biological systems., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The relevance of hydrogen-bonding, π-π stacking and aurophilic interactions in the solid-state of two new heterobimetallic (Au I -Mn II ) complexes is analyzed in this manuscript. They are discrete complexes of formulae [Mn(bipy) 2 (H 2 O){Au(CN) 2 }][Au(CN) 2 ] and [Mn(dmbipy) 2 {Au(CN) 2 }] ⋅ H 2 O, (bipy=2,2'-bipyridine and dmbipy=5,5'-dimethyl-2,2'-bipyridine), which are based on dicyanidoaurate(I) groups and 2,2'-bipyridyl-like co-ligands. They have been synthesized in good yields and X-ray characterized. In both compounds, aurophilic, OH⋅⋅⋅N hydrogen bonding and π-π interactions governed the supramolecular assemblies in the solid state. These contacts with special emphasis on the aurophilic interactions have been studied using density functional theory calculations and characterized using the quantum theory of atoms-in-molecules and the noncovalent interaction plot. The aurophilic contacts have been also rationalized from an orbital point of view using the natural bond orbital methodology, evidencing stabilization energies up to 5.7 kcal/mol. Moreover, the interaction energies have been decomposed using the Kitaura-Morokuma energy decomposition analysis, confirming the importance of electrostatic and orbital effects., (© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

After more than three decades of extensive investigations on supramolecular polymers, strategies for self-limiting growth still remain challenging. Herein, we exploit a new V-shaped monomer design to achieve anticooperatively formed oligomers with superior robustness and high luminescence. In toluene, the monomer-oligomer equilibrium is shifted to the monomer side, enabling the elucidation of the molecular packing modes and the resulting (weak) anticooperativity. Steric effects associated with an antiparallel staircase organization of the dyes are proposed to outcompete aromatic and unconventional B-F⋅⋅⋅H-N/C interactions, restricting the growth at the stage of oligomers. In methylcyclohexane (MCH), the packing modes and the anticooperativity are preserved; however, pronounced solvophobic and chain-enwrapping effects lead to thermally ultrastable oligomers. Our results shed light on understanding anticooperative effects and restricted growth in self-assembly., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Co-crystallization of 180°-orienting σ-hole-accepting tectons, namely, 1,4-diisocyanobenzene (1) and 1,4-diisocyanotetramethylbenzene (2), with such homoditopic halogen bond donors as 1,4-diiodotetrafluorobenzene (1,4-FIB) and 4,4'-diiodoperfluorobiphenyl (4,4'-FIBP) afforded co-crystals 1 ⋅ 1,4-FIB, 1 ⋅ 4,4'-FIBP, and 2 ⋅ 1,4-FIB. Their solid-state structures exhibit 1D-supramolecular arrangements, which are based on poorly explored I⋅⋅⋅C halogen bonding; this study is the first in which the supramolecular assembly utilizing halogen bonding with a terminal C atom was performed. The use of the potentially tetrafunctional σ-hole accepting tetraiodoethylene (TIE) leads to supramolecular architecture of a higher dimension, 3D-framework, observed in the structure of 1 ⋅ TIE. DFT calculations, used to characterize the halogen bonding situation, revealed that the I⋅⋅⋅C non-covalent interactions are moderately strong, ranging from -4.07 in 1 ⋅ TIE to -5.45 kcal/mol in 2 ⋅ 1,4-FIB. The NBO analysis disclosed that LP(C)→σ* charge transfer effects are relevant in all co-crystals., (© 2023 Wiley-VCH GmbH.)

Herein, the synthesis and X-ray structures of three α,β "two wall" aryl-extended calix[4]pyrroles having either identical (symmetrically substituted) or different (non-symmetrically substituted) meso-aryl substituents (aryl=4-ethynylphenyl and 4-iodophenyl) are reported. The X-ray structure of the co-crystal formed by the two symmetrically substituted calix[4]pyrroles is also described. In the solid state, all studied α,β-calix[4]pyrroles exhibit a 1,3-alternate conformation with two co-crystallized acetonitrile solvent molecules H-bonded to adjacent cis-pyrrole rings. Remarkably, the 1,3-conformer of the non-symmetrically substituted iodophenyl/ethynylphenyl compound is intrinsically chiral. The two enantiomers are present in the average asymmetric unit in a 65 : 35 occupancy ratio displaying a head-to-tail directional disorder. This is due to the functional complementarity and the isosteric and isoelectronic properties of the para-substituents: iodo and ethynyl. That is, the negative belt of iodine is similar to the negative π-system of the C≡C triple bond and the σ-hole in the iodine atom is similar to the positive proton at the C≡C-H group., (© 2022 Wiley-VCH GmbH.)

The co-crystallization of tetracyanobenzene (TCB) with haloarenes ArX provided six new co-crystals TCB ⋅ ArX (ArX=PhCl, PhBr, 4-MeC 6 H 4 Cl, 4-MeC 6 H 4 Br, 4-MeOC 6 H 4 Cl, 1,2-Br 2 C 6 H 4 ) which were studied by X-ray diffraction. In these systems, the strong collective effect of π⋅⋅⋅π stacking interactions and lone pair-(X)⋅⋅⋅π-hole-(C) bondings between TCB and ArX promote the strength of X⋅⋅⋅N cyano halogen bonding (HaB). Theoretical studies showed that the stacking interactions affect the σ-hole depth of the haloarenes, thus significantly boosting their ability to function as HaB donors. According to the molecular electrostatic potential calculations, the σ- hole-(Cl) value (1.5 kcal/mol) in the haloarene 4-MeOC 6 H 4 Cl (featuring an electron-rich arene moiety and exhibiting very poor σ-hole-(Cl) ability) increases significantly in the stacked trimer (TCB) 2  ⋅ 4-MeOC 6 H 4 Cl (12.5 kcal/mol). Theoretical DFT calculations demonstrate the dramatic increase of X⋅⋅⋅N cyano HaB strength for stacked trimers in comparison with parent unstacked haloarenes., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Hydrogen-bonded squaramide (SQ) supramolecular polymers exhibit uncommon thermoreversible polymorph transitions between particle- and fiber-like nanostructures. SQs 1-3, with different steric bulk, self-assemble in solution into particles (AggI) upon cooling to 298 K, and SQs 1 and 2, with only one dendronic group, show a reversible transformation into fibers (AggII) by further decreasing the temperature to 288 K. Nano-DSC and UV/Vis studies on SQ 1 reveal a concentration-dependent transition temperature and ΔH for the AggI-to-AggII conversion, while the kinetic studies on SQ 2 indicate the on-pathway nature of the polymorph transition. Spectroscopic and theoretical studies reveal that these transitions are triggered by the molecular reorganization of the SQ units changing from slipped to head-to-tail hydrogen bonding patterns. This work unveils the thermodynamic and kinetic aspects of reversible polymorph transitions that are of interest to develop stimuli-responsive systems., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In this study we propose to coin the term Wolfium bond (WfB) to refer to a net attractive force (noncovalent interaction) between any element of group 6 and electron donor atoms (neutral molecules or anions) and to differentiate it from a coordination bond (metal-ligand interaction). We provide evidence of the existence of this interaction by inspecting the X-ray crystal structure of proteins containing Molybdopterin and Tungstopterin cofactors from the Protein Data Bank (PDB). The plausible biological role of the interaction as well as its physical nature (antibonding Wf-Ligand orbital involved) are also analyzed by means of ab initio calculations (RI-MP2/def2-TZVP level of theory), Atoms in Molecules (AIM), Natural Bond Orbital (NBO) and Noncovalent Interactions plot (NCIplot) analyses., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report a series of rotaxane-based anion-π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

This review highlights recent studies discovering unconventional halogen bonding (HaB) that involves positively charged metal centers. These centers provide their filled d-orbitals for HaB, and thus behave as nucleophilic components toward the noncovalent interaction. This role of some electron-rich transition metal centers can be considered an oxymoron in the sense that the metal is, in most cases, formally cationic; consequently, its electron donor function is unexpected. The importance of Ha⋅⋅⋅d-[M] (Ha=halogen; M is Group 9 (Rh, Ir), 10 (Ni, Pd, Pt), or 11 (Cu, Au)) interactions in crystal engineering is emphasized by showing remarkable examples (reported and uncovered by our processing of the Cambridge Structural Database), where this Ha⋅⋅⋅d-[M] directional interaction guides the formation of solid supramolecular assemblies of different dimensionalities., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report the liquid-crystalline (LC) and luminescent properties of a series of N-annulated perylenes (1-4) in whose molecular structures amide and ester groups alternate. We found that the LC properties of these compounds not only depend on the number of hydrogen-bonding units, but also on the relative position of the amide linkers in the molecule. The absence of amide groups in compound 1 leads to no LC properties, whereas four amide groups induce the formation of a wide temperature range columnar hexagonal phase in compound 4. Remarkably, compound 3, with two amide groups in the inner part of the structure, stabilizes the columnar LC phases better than its structural isomer 2, with the amide groups in the outer part of the molecule. Similarly, we found that only compounds 1 and 2, which have no hydrogen bonding units in the inner part of the molecule, exhibit luminescence vapochromism upon exposure to organic solvent vapors., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

This communication reports experimental and theoretical evidences of σ-hole interactions in adducts between nitrogen or oxygen nucleophiles and tetroxides of osmium or other group 8 elements. Cocrystals between pyridine or pyridine N-oxide derivatives and osmium tetroxide are characterized through various techniques and rationalized as σ-hole interactions using DFT calculations and several other computational tools. We propose the term "osme bond" (OmB, Om=Fe, Ru, Os, (Hs)) for naming the noncovalent interactions wherein group 8 elements have the role of the electrophile. The word osme is the transcription of ὀσμή, the ancient Greek word for smell that was used to name the heaviest group 8 element in relation to the smoky odor of its tetroxide., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Interactions in crystalline tetrachloridoaurates of acetylcholine and dimethylpropiothetine are characterized by Au⋅⋅⋅Cl and Au⋅⋅⋅O short contacts. The former interactions assemble the AuCl 4 - units into supramolecular anionic polymers, while the latter interactions append the acetylcholine and propiothetine units to the polymer. The distorted octahedral geometry of the bonding pattern around the gold center is rationalized on the basis of the anisotropic distribution of the electron density, which enables gold to behave as an electrophile (π-hole coinage-bond donor). Computational studies prove that gold atoms in negatively charged species can function as acceptors of electron density. The attractive nature of the Au⋅⋅⋅Cl/O interactions described here complement the known aurophilic bonds involved in gold-centered interactions., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

An interplay between 4-bromo- and 4-iodo-5-nitrophthalonitriles (XNPN, X=Br or I) and any one of the azines (pyridine 1, 4-dimethylaminopyridine 2, isoquinoline 3, 4-cyanopyridine 4, 2-methylpyridine 5, 2-aminopyridine 6, quinoline 7, 1-methylisoquinoline 8, and 2,2'-bipyridine 9) proceeds differently depending on steric and electronic effects of the heterocycles. Sterically unhindered azines 1-3 underwent N-arylation to give the corresponding azinium salts (characterized by 1 H and 13 C{H} NMR and high-resolution ESI-MS). In contrast, azines 4-9 with sterically hindered N atoms or bearing an electron-withdrawing substituent, form stable co-crystals with XNPN, where two interacting molecules are bound by halogen bonding. In all obtained co-crystals, X⋅⋅⋅N structure-directed halogen bonds were recognized and theoretically evaluated including DFT calculations (PBE0-D3/def2-TZVP level of theory), QTAIM analysis, molecular electrostatic potential surfaces, and noncovalent interaction plot index. Estimated energies of halogen bonding vary from -7.6 kcal/mol (for 6 ⋅ INPN) to -11.4 kcal/mol (5 ⋅ INPN)., (© 2021 Wiley-VCH GmbH.)

Naphthalenediimides (NDIs) are privileged scaffolds par excellence, of use in functional systems from catalysts to ion channels, photosystems, sensors, ordered matter in all forms, tubes, knots, stacks, sheets, vesicles, and colored over the full visible range. Despite this extensively explored chemical space, there is still room to discover core-substituted NDIs with fundamentally new properties: NDIs with cyclic trisulfides (i.e., trisulfanes) in their core absorb at 668 nm, emit at 801 nm, and contract into disulfides (i.e., dithietes) upon irradiation at <475 nm. Intramolecular 1,5-chalcogen bonds account for record redshifts with trisulfides, ring-tension mediated chalcogen-bond-mediated cleavage for blueshifts to 492 nm upon ring contraction. Cyclic oligochalcogenides (COCs) in the NDI core open faster than strained dithiolanes as in asparagusic acid and are much better retained on thiol exchange affinity columns. This makes COC-NDIs attractive not only within the existing multifunctionality, particularly artificial photosystems, but also for thiol-mediated cellular uptake., (© 2020 Wiley-VCH GmbH.)

The term spodium (Sp) bond is proposed to refer to a net attractive interaction between any element of Group 12 and electron-rich atoms (Lewis bases or anions). These noncovalent interactions are markedly different from coordination bonds (antibonding Sp-ligand orbital involved). Evidence is provided for the existence of this interaction by calculations at the RI-MP2/aug-cc-pVTZ level of theory, atoms-in-molecules, and natural bond orbital analyses and by examining solid-state structures in the Cambridge Structure Database., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

1,1,2,2-Tetracyanocyclopropane derivatives 1 and 2 were designed and synthesized to probe the utility of sp 3 -C centred tetrel bonding interactions in crystal engineering. The crystal packing of 1 and 2 and their 1,4-dioxane cocrystals is dominated by sp 3 -C(CN) 2 ⋅⋅⋅O interactions, has significant C⋅⋅⋅O van der Waals overlap (≤0.266 Å) and DFT calculations indicate interaction energies of up to -11.0 kcal mol -1 . A cocrystal of 2 with 1,4-thioxane reveals that the cyclopropane synthon prefers interacting with O over S. Computational analyses revealed that the electropositive C 2 (CN) 4 pocket in 1 and 2 can be seen as a strongly directional 'tetrel-bond donor', similar to halogen bond or hydrogen bond donors. This disclosure is expected to have implications for the utility of such 'tetrel bond donors' in molecular disciplines such as crystal engineering, supramolecular chemistry, molecular recognition and medicinal chemistry., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The theoretical data for the half-lantern complexes [{Pt( C N ^ )(μ- S N ^ )} 2 ] [1-3; C N ^ is cyclometalated 2-Ph-benzothiazole; S N ^ is 2-SH-pyridine (1), 2-SH-benzoxazole (2), 2-SH-tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer d z 2 orbitals to provide assembly with electrophilic species. Complexes 1-3 were co-crystallized with bifunctional halogen bonding (XB) donors to give adducts (1-3) 2 ⋅(1,4-diiodotetrafluorobenzene) and infinite polymeric [1⋅1,1'-diiodoperfluorodiphenyl] n . X-ray crystallography revealed that the supramolecular assembly is achieved through (Aryl)I⋅⋅⋅d z 2 [Pt II ] XBs between iodine σ-holes and lone pairs of the positively charged (Pt II ) 2 centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt 2 ⋅⋅⋅I(arene F )I⋅⋅⋅Pt 2 ⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (Pt II ) 2 moieties. The 195 Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D) 2 Cl 2 solutions., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The utilization of neutral receptors for the molecular recognition of anions based on chalcogen bonding (ChB) is an undeveloped area of host-guest chemistry. In this manuscript, the synthesis of two new families of sulfur, selenium, and tellurium-based ChB binding motifs are reported. The stability of the thiophene, selenophene, and tellurophene binding motifs has enabled the determination of the association constants for ChB halide anion binding in the polar aprotic solvent THF by 1 H, 77 Se, and 125 Te NMR experiments. Two different aromatic cores are used and one or two Ch-binding motifs are incorporated with the purpose of encapsulating the anion, offering up to two concurrent chalcogen bonds. Theoretical calculations and NMR experiments reveal that, for S and Se receptors, hydrogen-bonding interactions involving the acidic H atom adjacent to the chalcogen atom are energetically favored over the ChB interaction. However, for the tellurophene binding motif, the σ-hole interaction is competitive and more favored than the hydrogen bond., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Invited for the cover of this issue are the groups of Antonio Frontera at the Universitat de les Illes Balears and Antonio Caballero at the Universidad de Murcia. The image depicts one of the tellurophene based receptors described in this work. Read the full text of the article at 10.1002/chem.201905786., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study reports a combined Cambridge Structural Database and theoretical DFT study of charge assisted chalcogen bonds involving sulfonium, selenonium, and telluronium cations. The chalcogen bond has been recently defined by IUPAC as the net attractive interaction between an electrophilic region associated with a chalcogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Divalent chalcogen atoms typically have up to two σ-holes and forms up to two ChBs; the same holds for tetravalent chalcogens which adopt a seesaw arrangement. In sulfonium, selenonium, and telluronium salts chalcogen atoms form three covalent bonds, three σ-holes are located opposite to these bonds, and up to three charge assisted ChBs can be formed between these holes and the counterions. The covalent bond arrangement around these chalcogen atoms is similar to trivalent pnictogen atoms and translates into a similar pattern of noncovalent interactions. We have found and studied this type of charge-assisted chalcogen bonds in various sulfonium ion-containing inhibitors of glucosidase, for example, salacinol and kotalanol., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two mononuclear uranyl complexes, [UO 2 L 1 ] (1) and [UO 2 L 2 ]⋅0.5 CH 3 CN⋅0.25 CH 3 OH (2), have been synthesized from two multidentate N 3 O 4 donor ligands, N,N'-bis(5-methoxysalicylidene)diethylenetriamine (H 2 L 1 ) and N,N'-bis(3-methoxysalicylidene)diethylenetriamine (H 2 L 2 ), respectively, and have been structurally characterized. Both complexes 1 and 2 showed a reversible U VI /U V couple at -1.571 and -1.519 V, respectively, in cyclic voltammetry. The reduction potential of the U VI /U V couple shifted towards more positive potential on addition of Li + , Na + , K + , and Ag + metal ions to acetonitrile solutions of complex 2, and the resulting potential was correlated with the Lewis acidity of the metal ions and was also justified by theoretical DFT calculations. No such shift in reduction potential was observed for complex 1. All four bimetallic products, [UO 2 L 2 Li 0.5 ](ClO 4 ) 0.5 (3), [UO 2 L 2 Na(ClO 4 )] 2 (4), [UO 2 L 2 Ag(NO 3 )(H 2 O)] (5), and [(UO 2 L 2 ) 2 K(H 2 O) 2 ]PF 6 (6), formed on addition of the Li + , Na + , Ag + , and K + metal ions, respectively, to acetonitrile solutions of complex 2, were isolated in the solid state and structurally characterized by single-crystal X-ray diffraction. In all the species, the inner N 3 O 2 donor set of the ligand encompasses the equatorial plane of the uranyl ion and the outer open compartment with O 2 O' 2 donor sites hosts the second metal ion., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Studying noncanonical intermolecular interactions between a ligand and a protein constitutes an emerging research field. Identifying synthetically accessible molecular fragments that can engage in intermolecular interactions is a key objective in this area. Here, it is shown that so-called "π-hole interactions" are present between the nitro moiety in nitro aromatic ligands and lone pairs within protein structures (water and protein carbonyls and sulfurs). Ample structural evidence was found in a PDB analysis and computations reveal interaction energies of about -5 kcal mol -1 for ligand-protein π-hole interactions. Several examples are highlighted for which a π-hole interaction is implicated in the superior binding affinity or inhibition of a nitro aromatic ligand versus a similar non-nitro analogue. The discovery that π-hole interactions with nitro aromatics are significant within protein structures parallels the finding that halogen bonds are biologically relevant. This has implications for the interpretation of ligand-protein complexation phenomena, for example, involving the more than 50 approved drugs that contain a nitro aromatic moiety., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The importance of anion-π interactions as a driving force for chemical and biological processes is increasingly being recognized. In this communication, we describe for the first time its key participation in light-induced reactions. We show, in particular, how transient complexes formed through noncovalent anion-π interactions between electron-poor N-aryloxyamides and multiply-charged anions (such as carbonate or phosphate) can undergo facile light-promoted N-O cleavage, affording amidyl radicals that can subsequently be trapped by (hetero)aromatics., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A molecular Solomon link adopts different conformations in acetonitrile (1) and in water (2). Contrary to expectations, the main driving force of the transformation is not the change in medium polarity, but the cooperative binding of about four molecules of water, forming a tiny droplet in the central cavity of 2. Mechanistic studies reveal that the four binding sites can simultaneously switch between an inactive state (unable to bind water) and an active state (able to bind water) during the transformation. Spatial and temporal coordination of switching events is commonly observed in biological systems but has been rarely achieved in artificial systems. Here, the concerted activation of the four switchable sites is controlled by the topology of the whole molecule., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The ability of tetrahedral lead(IV) to establish noncovalent σ-hole tetrel bonding interactions with electron-rich atoms (ElRs; anions and Lewis bases) has been studied at the PBE0-D3/def2-TZVPD level of theory. An analysis of the Cambridge Crystallographic Database (CSD), which is a convenient storehouse of geometric information, has been performed to investigate the existence of tetrel bonding interactions involving tetrahedral lead(IV) derivatives. Several examples of tetrel bonding interactions that are crucial in crystal packing, ranging from 0D to 2D assemblies, have been found. In addition to the energetic and theoretical study of several XPb(CH 3 ) 3 ⋅⋅⋅ElR complexes (X=F, CN, CF 3 , and CH 3 ), Bader's theory of atoms in molecules has also been used to further analyze and characterize the noncovalent interactions described herein., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, a PDB (Protein Data Bank) analysis and theoretical calculations (PBE0-D3/def2-TZVP level of theory) were combined to analyze the impact of S⋅⋅⋅Sn tetrel-bonding interactions in the activation mechanism of peroxisome proliferator-activated receptors (PPARs) by two organotin derivatives, triphenyltin (TPT) and tributyltin (TBT). The presence of a covalently bonded CYS285 to the organotin molecule was found to be key to enhance the σ-hole-donor ability of the tin atom, thus strengthening the tetrel-bonding interaction with a sulfur atom belonging to a vicinal methionine residue (MET364)., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scope: Resveratrol (RSV) and nicotinamide riboside (NR) are food compounds with anti-obesity actions in adult rodents. Here, the long-term effects of RSV and NR mild supplementation throughout lactation on adiposity-related parameters and the appearance of the beige phenotype in white adipose tissue (WAT) in adulthood are assessed., Methods and Results: Newborn mice received orally RSV or NR from day 2 to 20 of life. Control littermates received the vehicle. All animals are weaned onto a chow diet on day 21. On day 90, half the animals of each group are assigned to a high-fat diet (HFD) for 10 weeks, while the other remained on a normal-fat diet. Energy-balance-related parameters, blood parameters, and gene expression and immunohistochemical analysis of WAT are assessed. Treated male mice show an improved response to the HFD, such as delayed body weight gain, a blunted increase in the plasma leptin/adiponectin ratio, and a decreased lipolytic response, together with signs of white-to-brown fat remodeling in inguinal WAT. These effects are absent in female mice., Conclusion: RSV and NR supplementations in early postnatal life affect WAT's thermogenic/oxidative transcriptional phenotype and metabolic responses in adulthood, with upregulatory and beneficial effects evidenced in male animals., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The ability of Fe 3 O 4 magnetic nanoparticles decorated with perylene bisimides to adsorb aromatic volatile organic compounds (VOCs) is reported. We have used DFT-D3 calculations to anticipate the strong ability of the electron-poor perylene bisimide to form noncovalent complexes with electron-rich aromatic rings belonging to the VOC family. Subsequently, we synthesized a hybrid magnetic nanomaterial based on bisimide perylene dopamine and iron oxide nanoparticles. This material was used to fill a sorbent tube to study its ability to adsorb aromatic VOCs. We connected two tubes in series filled with the hybrid nanoparticles. The analysis of the front and back tubes was performed by thermal desorption (TD) coupled with capillary gas chromatography (GC)/flame ionization detector (FID). Adsorption values (defined as %VOCs found in the back tube) were determined for a series of aromatic VOCs and compared with the DFT binding energies. The tubes can be desorbed and reutilized more than 200 times without losing their properties., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Noncovalent carbon bonding, a recently explored σ-hole interaction, was hitherto supposed to be a weak and structure-guided interaction. Here, its role in the intramolecular stabilization of the cis conformation of the amide moiety in acylhydrazones is described. The calculations reveal an electron donation from the lone pair of the nitrogen atom to the empty antibonding C-N orbital [LP(N)→BD*(C-N)] with a concomitant stabilization energy of E (2) =1.2 kcal mol -1 ., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The design, synthesis and evaluation of catalytic triads composed of a central C 60 fullerene with an amine base on one side and polarizability enhancers on the other side are reported. According to an enolate addition benchmark reaction, fullerene-fullerene-amine triads display the highest selectivity in anion-π catalysis observed so far, whereas NDI-fullerene-amine triads are not much better than fullerene-amine controls (NDI=naphthalenediimide). These large differences in activity are in conflict with the small differences in intrinsic π acidity, that is, LUMO energy levels and π holes on the central fullerene. However, they are in agreement with the high polarizability of fullerene-fullerene-amine triads. Activation and deactivation of the fullerene-centered triads by intercalators and computational data on anion binding further indicate that for functional relevance, intrinsic π acidity is less important than induced π acidity, that is, the size of the oriented macrodipole of polarizable π systems that emerges only in response to the interaction with anions and anionic transition states. The resulting transformation is thus self-induced, the anionic intermediates and transition states create their own anion-π catalyst., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The ability of metal clusters involving elements from group 11 (Ag, Cu, Au) to favorably interact with π systems of different size and electronic nature was evaluated at the PBE0-D3/def2-TZVPP//PBE0-D3/def2-TZVP level of theory. The M 9 clusters (M=Cu, Ag, Au) were used as σ-hole and σ-lump donors, and benzene, trifluorobenzene, and hexafluorobenzene as aromatic rings. In addition, the study was expanded to the analysis of extended π systems by using naphthalene and anthracene as well as their corresponding perfluorinated derivatives. Furthermore, Bader's theory of Atoms in Molecules as well as natural bonding orbital and spin-density calculations were used to further investigate and characterize the regium-π and σ-lump complexes described herein. Apparently, regium-π bonds have not previously been described in the literature and may be of great importance in the understanding of organocatalytic processes involving aromatic substrates as well as in the design of new materials based on this novel subclass of σ-hole bonding., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tri(phosphonio)methanide dication 3 2+ , prepared from a trifluoromethylsulfanylphosphonium dication (1 2+ ) via an intramolecular electrophilic aromatic substitution reaction, is an unexpected P-based, water-resistant Lewis acid that is capable to selectively and reversibly bind fluoride ions from organic/aqueous biphasic solution. The formed complex is an unusual fluorophosphorane ([3-F]OTf). The multiple donor-acceptor interactions of 3 2+ that are crucial for the fluoride fixation have been elucidated by quantum chemical calculation. Compound [3-F]OTf can also be used as a convenient anhydrous fluoride ion source and was probed as a suitable catalyst of the silylotrifluoromethylation of various aldehydes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)