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In recent years, optical temperature probes operating in the second near-infrared (BW-II) and third near-infrared (BW-III) biological windows have garnered significant attention in the scientific community. For biological applications these probes offer distinct advantages, including enhanced tissue penetration depth, minimal autofluorescence, and a remarkable improvement in imaging sensitivity and spatial resolution. Moving toward theranostic applications, there is a growing demand for the development of materials that integrate both BW-II and BW-III thermometry systems with drug delivery functionalities. In this study, we concentrate on the development of GdPO4materials, utilizing both hard and sacrificial template routes to synthesize (hollow) GdPO4porous sea urchin-like particles. We first investigated the development of a Boltzmann-type thermometer utilizing an Yb–Er upconversion system, designed to operate within the physiological temperature range. Our exploration extends to the potential of GdPO4particles in near-infrared (NIR) thermometry, spanning the first, second, and third biological windows with systems like Yb–Ho–Er, Nd–Yb, and Ho–Yb, respectively. We further examined the temperature impact of the Yb–Ho–Er system on the NIR emission within a biologically relevant setting, using a phantom that replicates biological tissue. Furthermore, we illustrate the successful loading of these materials with doxorubicin (DOX·HCl), a model anticancer drug, showing these particles exhibit pH-dependent DOX release. This demonstrates the versatility of these materials as upconversion and NIR thermometers while simultaneously serving as an on-demand drug carrier. The investigation involves assessing their cytotoxicity on specific human cells (Normal Human Dermal Fibroblasts (NHDFs)), to determine their viability for potential use in biological applications. The study also investigates how effectively loading the particles with DOX enables targeted delivery to a cellular model of lymphoma (Jurkat E6-1), resulting in cell death. This comprehensive analysis highlights the promising potential of GdPO4particles for medical applications.

The gold(I)-catalyzed dearomative cyclopentannulation of various indoles with 2-ethynyl-1,3-dithiolane is reported. The method generates three new stereocenters with excellent control of relative stereochemistry and is tolerant of diverse functionalization and substitution patterns on the indoles. The obtained cyclopentane-fused indolines allow for interesting subsequent synthetic manipulations, giving rise to fully substituted cyclopentanes with control of the relative stereochemistry of all five stereocenters. The reported reaction illustrates and elucidates a mechanistic dichotomy underlying gold(I)-catalyzed reactions of 2-ethynyl-1,3-dithiolane.

Defect engineering in metal–organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO2and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.

Two-dimensional (2D) hybrid organic–inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces. Here, we report a more complex organic sublattice containing benzotriazole-based ammonium cations packed through interdigitated π–π stacking and hydrogen bonding. Single crystals and thin films of four perovskite derivatives are studied in depth with optical spectroscopy and X-ray diffraction, supported by density-functional theory calculations. We quantify the lattice stabilization of interdigitation, dipole–dipole interactions, and inter- as well as intramolecular hydrogen bonding. Furthermore, we investigate the driving force behind interdigitation by defining a steric occupancy factor σ and tuning the composition of the organic and inorganic sublattice. We relate the phenomenon of interdigitation to the available lattice space and to weakened hydrogen bonding to the inorganic octahedra. Finally, we find that the stabilizing interactions in the organic sublattice slightly improve the thermal stability of the perovskite. This work sheds light on the design rules and structure–property relationships of 2D layered hybrid perovskites.

In this study, we report hybrid crystalline lanthanide-containing 3D covalent organic framework (Ln@3D COF) materials that are suitable for temperature sensing applications. Different routes to obtain these hybrid materials were tested and compared for material quality and thermometric properties. In the first approach, a bipyridine-containing 3D COF (Bipy COF) was grafted with a range of visible emitting lanthanide (Eu3+, Tb3+, Dy3+, and Eu3+/Tb3+) β-diketonate complexes. In the second approach, a novel nanocomposite material was prepared by embedding NaYF4:Er,Yb nanoparticles on the surface of a nonfunctionalized 3D COF (COF-300). To the best of our knowledge, the luminescent materials developed here are the first 3D COFs to be tested as ratiometric temperature sensors. In fact, for the Bipy COF, two different types of thermometers were tested (the Eu3+/Tb3+system and a rare Dy3+system), with both showing excellent temperature sensing properties. The reported NaYF4:Er,Yb/COF-300 nanocomposite material combines upconverting nanoparticles with 3D COFs, similar to previously reported metal organic framework (MOF) nanocomposite materials; however, this type of hybrid material has not yet been explored for COFs. As such, our findings open a new pathway toward potential multifunctional materials that can combine thermometry with other modalities, such as catalysis or drug delivery, in just one nanocomposite material.

Thiophene, a key building block for the construction of conjugated materials, has been scarcely studied in halogen bonding (XB)-driven self-assemblies. In the present study, two thiophene derivatives modified at position 3 were (co-)crystallized using complementary XB donor/acceptor functional groups. Single-crystal X-ray diffraction analysis confirmed the presence of halogen and chalcogen bonding acting, in most cases, concomitantly. While the majority of the structures are governed by the conventional N···I motif, additional S···N and S···S contacts encouraged the cohesion of the supramolecular architectures. Density functional theory calculations shed the light on interaction energy, their respective contributions of the motifs to these non-covalent bonds, and the overall stability of these assemblies. To gain further insight into the formation and evidence of XB interactions, solution and mechanochemical syntheses of polymorphic adducts were performed, followed by 13C solid-state NMR analysis. Further, 1H and 19F{1H} solution-state NMR spectroscopy studies were carried out to highlight these interactions in the solution phase. The strength and directionality of halogen bonding thus reaffirm its role as a structure-directing agent for designing functional materials. The evidence of N···S chalcogen bonds in thiophene derivatives also broadens up the horizon of supramolecular chemistry in S-heterocycles, while necessitating further investigation for rational application in materials science.

The development of efficient and operationally simple synthetic routes to dinuclear gold(i)-amido complexes bearing aromatic/aliphatic-bridges are reported. This family of complexes was prepared utilizing environmentally friendly and sustainable reagents under mild conditions, resulting in 68–92% yields of the targeted compounds. These novel dinuclear gold(i)-amido complexes were structurally and spectroscopically characterized. Their photophysical properties were also studied. This series of gold complexes are phosphorescent with lifetimes in the hundreds of microseconds range. They exhibit high catalytic activity as photosensitizers in intramolecular cycloaddition and cyclization reactions at catalyst loadings ranging from 0.5 to 2 mol%.

The present study delves into the synthesis and characterization of multi-stimuli responsive polymers, demonstrating their sensitivity towards magnetic field, pH level, light irradiation, and electron-rich species through halogen bonding (XB). Detailed X-ray analyses of two azobenzene derivatives, each incorporating a tetrafluoroiodobenzene group, provided the compelling evidence of engagement of the building blocks in the formation of halogen bonds. Interestingly, the investigation of an ammonium analog, featuring a tetrahalogenoferrate(III) anion, not only showcased a magnetic response even upheld its ability to undergo isomerization under UV irradiation. These functional properties were subsequently harnessed in the form of multi-responsive compounds through the random quaternization of poly(2-(N,N-dimethylamino) ethyl methacrylate) (PDMAEMA), and by employing varying proportions of XB-donor dye (8, 11, 15, 21, and 43 %) followed by magnetic anion exchange. Leveraging the presence of free ternary amino groups and diazobenzene moieties, the resulting polymers demonstrated pronounced sensitivity towards a variation of pH and UV light stimuli, while a careful modulation of magnetic susceptibility was found to be directly proportional to the degree of quaternization. An NMR titration, conducted using a synthetic intermediate, revealed the formation of I⋯Cl‾ interactions in the solution state, thereby underscoring the materials' sensitivity to electron-rich species. Moreover, the electron microscopic analysis displayed an alteration in morphology upon the application of a magnetic field and UV irradiation. Thus, the presented strategic framework offers an avenue for the development of multi-stimuli responsive materials for remotely controlled smart devices to act in response to a diverse set of four stimuli, and heralding a significant advancement in the realm of responsive material design.

The (3 + 2) cycloaddition of various indoles with a dithioallyl cation affords dearomatized cyclopentannulated adducts, with complete control of regioselectivity and excellent chemo- and diastereoselectivity. The success of the reaction critically relies on the use of an excess of very strong Brønsted acid, which paradoxically prevents carbocationic side reactions. The reaction tolerates sensitive functionalities such as basic amines or free hydroxyls, and we demonstrate its use in late stage derivatization of highly functionalized, unprotected indoles.

A simple and efficient method for the oxidative coupling of terminal alkynes is reported for the first time, making use of imidazol(in)ium aurates as pre-catalysts. This approach displays high functional group tolerance and leads to a broad range of 1,3-diyne compounds in moderate to excellent yields using low catalyst loading and is performed in air under mild and sustainable conditions.

Macro- and nanosized core, as well as core–shell, γ-cyclodextrin metal–organic frameworks (γ-CD-MOFs) have been designed and used as platforms for the encapsulation of dye molecules to develop the first CD-MOF-based ratiometric optical thermometer materials. A novel dye combination was employed for this purpose, i.e., the duo rhodamine B (RhB) and fluorescein (FL). RhB is highly temperature-sensitive, whereas FL is less temperature-sensitive, and its luminescence emission peak is used as a reference. Promising results in terms of thermometric properties were obtained for a series of dye-encapsulated γ-CD-MOF materials based on this dye combination, with high relative sensitivities, even up to 5%K–1, for the dye-encapsulated 75%RhB-25%FL nanosized γ-CD-MOF, among the highest performance values reported so far for luminescent dual thermometers. In our study, we have additionally developed a simple yet effective preparation method for core–shell γ-CD-MOFs, allowing effective manipulation of the γ-CD-MOF shell growth. The proposed method allows incorporation of the FL and RhB dyes in the γ-CD-MOFs in a more controlled manner, enhancing the efficiency of the developed ratiometric (macro) γ-CD-MOF thermometers.

At present, two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) are drawing significant interest because of their potential use in different optoelectronic applications, that is, photovoltaics and photodetectors. Here, we report on a series of 2D layered HOIPs (Bit-C3)2PbX4(with X = Cl, Br, and I) containing a 2,2′-bithiophene chromophore functionalized with a propylammonium tethering chain as a model molecule. The optical properties, crystal structure, and phase behavior of the 2D layered HOIPs are studied in depth. The crystal structures with the chemical formula (Bit-C3)2PbX4(with X = Cl, and Br) are successfully obtained. Contrastingly, different crystal structures with an inorganic framework containing face- and corner-sharing octahedra were identified for the iodide-based HOIP. The phase diversity and thermal stability of the (Bit-C3)2PbX4(with X = Cl, Br, and I) thin films were investigated via in situmeasurements. Here, the presence of lower-dimensional hybrids with reduced electronic dimensionality within the iodide-based thin film is demonstrated. Additionally, we show that the 2D hybrid thermal stability is dependent on the type of lead(II)halide framework employed. We suggest that, via halide substitution from iodide to bromide and chloride, the molecular degrees of freedom of the Bit-C3 ammonium cations are reduced by spatial confinement of a smaller inorganic framework, therefore, limiting the formation of lower-dimensional hybrids besides the targeted 2D layered HOIP. This study illustrates the importance of efficiently utilizing the space supplied by the inorganic framework in which the organic ammonium cations can reside within a 2D layered HOIP. This, in turn, dictates how the organic ammonium cations arrange themselves within the organic layer and influences the adopted crystal structure of the hybrid.

Cation–dipole interactions were previously shown to have a rate-enhancing effect on the cationic ring-opening polymerization (CROP) of 2-oxazolines bearing a side-chain ester functionality. In line with this, a similar rate enhancement—via intermolecular cation−π interactions—was anticipated to occur when π-bonds are introduced into the 2-oxazoline side-chains. Moreover, the incorporation of π-bonds allows for facile postfunctionalization of the resulting poly(2-oxazoline)s with double and triple bonds in the side-chains via various click reactions. Herein, a combined molecular modeling and experimental approach was used to study the CROP reaction rates of 2-oxazolines with side-chains having varying degrees of unsaturation and side-chain length. The presence of cation−π interactions and the influence of the degree of unsaturation were initially confirmed by means of regular molecular dynamics simulations on pentameric systems. Furthermore, a combination of enhanced molecular dynamics simulations, static calculations, and a thorough analysis of the noncovalent interactions was performed to unravel to what extent cation−π interactions alter the reaction kinetics. Additionally, the observed trends were confirmed also in the presence of acetonitrile as solvent, in which experimentally the polymerization is performed. Most intriguingly, we found only a limited effect on the intrinsic reaction kinetics of the CROP and a preorganization effect in the reactive complex region. The latter effect was established by the unsaturated side-chains and the cationic center through a complex interplay between cation−π, π–π, π–induced dipole, and cation–dipole interactions. These findings led us to propose a two-step mechanism comprised of an equilibration step and a CROP reaction step. The influence of the degree of unsaturation, through a preorganization effect, on the equilibration step was determined with the following trend for the polymerization rates: n-ButylOx < ButenOx < ButynOx ≥ PentynOx. The trend was experimentally confirmed by determining the polymerization rate constants.

The present study highlights a straightforward and versatile strategy for the synthesis of strong poly(2-isopropenyl-2-oxazoline) hydrogels with tunable properties by using a bifunctional macrocyclic pillar[5]arene host having two carboxylic acid groups as cross-linker. This new strategy provides access to materials with tailored properties from soft and flexible to rigid and strong. The mechanical properties and water uptake of the hydrogels could be effortlessly controlled during the synthesis step through variation of the cross-linker content and after cross-linking by guest–host interactions. The hydrogels displayed strongly enhanced mechanical properties (i.e., compression and tensile modulus, energy dissipation, stress at break and storage modulus) compared to their counterparts cross-linked with linear dicarboxylic acids. The remarkable properties of the pillar[5]arene cross-linked hydrogels were assigned to the transfer of the external stress to the rigid and bulky pillar[5]arene residues that contribute to the overall dimensional stability of the hydrogels and allow energy dissipation. Moreover, we demonstrate the applicability of these materials for water purification. The hydrogels showed high adsorption performance for phenols and dyes such as methylene blue and methyl red and they could be easily regenerated, by washing with an organic solvent for reuse.

Covalent organic frameworks (COFs) have gained a lot of attention in recent years due to their tunable porosity and functionality. Porphyrin-containing COFs have proven effective in several applications such as photo- and electrocatalysis. However, a standard reproducible procedure for the synthesis of crystalline metalated porphyrin COFs remains challenging. In this work, a general procedure using an “assembler” approach based on preorientation is reported. Octahedrally coordinating metal ions were used along with pyridinic ligands in addition to the starting monomers of the COF in a one-pot synthesis method to produce crystalline metalated porphyrin COFs with high surface area and reproducibility. Different metals, assemblers, and assembler loadings were studied, and their performances are compared. This method allows the production of high-quality porphyrin COFs which are useful for a range of applications such as catalysis, sensor technology, energy storage, and photodynamic therapy.

Enantiopure 4-formyl-β-lactams were deployed as synthons for the diastereoselective formation of chiral 2-(2,2,2-trifluoro-1-hydroxyethyl)azetidines via trifluoromethylation through aldehyde modification followed by reductive removal of the β-lactam carbonyl moiety. Subsequent treatment of the (in situ) activated 2-trifluoroethylated azetidines with a variety of nitrogen, oxygen, sulfur, and fluorine nucleophiles afforded chiral 3,4-disubstituted 2-(trifluoromethyl)pyrrolidines in good to excellent yields (45–99%) and high diastereoselectivities (dr >99/1, 1H NMR) via interception of bicyclic aziridinium intermediates. Furthermore, representative pyrrolidines were N,O-debenzylated in a selective way and used for further synthetic elaboration to produce, for example, a CF3-substituted 2-oxa-4,7-diazabicyclo[3.3.0]octan-3-one system.

The solid-state synthesis of single-crystalline organic polymers, having functional properties, remains an attractive and developing research area in polymer chemistry and materials science. However, light-triggered topochemical synthesis of crystalline polymers comprising an organoboron backbone has not yet been reported. Here, we describe an intriguing example of single-crystal-to-single-crystal (SCSC) rapid photosynthesis (occurs on a seconds-scale) of two structurally different linear organoboron polymers, driven by environmentally sustainable visible/sun light, obtained from the same monomer molecule. A newly designed Lewis acid–base type molecular B ← N organoboron adduct (consisting of an organoboron core and naphthylvinylpyridine ligands) crystallizes in two solid-state forms featuring the same chemical structure but different 3D structural topologies, namely, monomers 1and 2. The solvate molecule-free crystals of 1undergo topochemical photopolymerization via an unusual olefin–naphthyl ring [2 + 2] cyclization to yield the single crystalline [3]-ladderane polymer 1Pgrowing along the B ← N linkages, accompanied by instantaneous and violent macroscopic mechanical motions or photosalient effects (such as bending-reshaping and jumping motions). In contrast, visible light-harvesting single crystals of 2quantitatively polymerize to a B ← N bond-stabilized polymer 2Pin a SCSC fashion owing to the rapid [2 + 2] cycloaddition reaction among olefin double bonds. Such olefin bonds in the crystals of 2are suitably preorganized for photoreaction due to the presence of solvate molecules in the crystal packing. Single crystals of 2also show photodynamic jumping motions - in response to visible light but in a relatively slower fashion than the crystals of 1. In addition to SCSC topochemical polymerization and dynamic motions, both monomer crystals and their single-crystalline polymers feature green emissive and short-lived room-temperature phosphorescence properties upon excitation with visible-light wavelength.

The self-assembly of Zn(II), Cd(II), or Hg(II) salts with long flexible 1,2,4-triazole-based ligands resulted in coordination polymers and mononuclear complexes of diverse topology. Indeed, the 1D chain [ZnCl2(btpm)] (1) (P1̅), the 2D square grid [Zn(btpm)2(H2O)](BF4)2·2btpm·8H2O (2) (P21212), and the 1D chain [Cd3Cl6(btpm)2]·8H2O (3) (P1̅) with btpm= bis(4-(1,2,4-triazol-4-yl)phenyl)methane were crystallized. In addition, the mononuclear complexes [ZnCl2(ppt)2] (4) (I2) and [HgBr2(ppt)2] (5) (C2) were obtained along with the 1D polymer [Cd2Cl2(ppt)4](CdCl4)·4DMF (6) (P1) with ppt= (4-phenoxyphenyl)-1,2,4-triazole. 1D chains of the formula [ZnCl2(tpca)] (7) (P21/c) and [HgBr2(tpca)] (8) (P21/c) along with the 2D net [Cd(tpca)2(H2O)2]·2H2O (C2/c) (9) with tpca= N-(1,2,4-triazol-4-yl)pyridine-3-carboxamide were obtained. In addition, the X-ray structures of tpcaand pptare described. All compounds display solid-state blue luminescence, which has been investigated in detail. Electrochemical synthesis of 2, which has been rarely applied for MOF synthesis, revealed hollow particles.

The method and results described herein concern the photosensitized addition of various alcohols to renewable platform fumaric and itaconic acids under scalable continuous-flow conditions in glass micro- and mesofluidic reactors. Alcohols were used both as reagents and as solvents, thus contributing to a reduced environmental footprint. Process parameters such as the temperature, light intensity, and the nature as well as amount of the photosensitizer were assessed under microfluidic conditions and, next, transposed to a lab-scale mesofluidic reactor connected with an in-line NMR spectrometer for real-time reaction monitoring. Substituted γ-butyrolactones, including spiro derivatives with unique structural features, were obtained with quantitative conversion of the starting materials and in 47–76% isolated yields. The model photoaddition of isopropanol to fumaric acid was next successfully transposed in a pilot-scale continuous-flow photoreactor to further demonstrate scalability.

The reaction of pyridine-2,4-dicarboxylic acid (2,4-H2pydc) with Ce(NO3)3·6H2O, by applying only minor changes to the reaction conditions, generated a series of new one-, two-, and three-dimensional (1D, 2D, and 3D) coordination polymers, namely, [Ce(pydc)(Hpydc)(H2O)4]n(1), [Ce(pydc)(Hpydc)(H2O)2]n(2), and {[Ce3(pydc)4(H2O)2NO3]·4H2O}n(3). The ancillary ligand interaction as well as the reaction conditions determine the specific coordination modes for the Hpydc–and pydc2–ligands and, in turn, discriminate between 1D, 2D, and 3D frameworks. Characterization of the prepared materials was performed using single-crystal and powder X-ray diffraction analysis, Fourier transform infrared spectroscopy, CHN elemental analysis, thermogravimetric analysis, and nitrogen adsorption/desorption techniques. Compound 1consists of 1D chains, that compose of Ce3+ions bridged by Hpydc–and pydc2–ligands, which further link via noncovalent interactions to form a 3D supramolecular architecture. Compound 2assembles into 2D sheets with 1D channels. Similarly, via hydrogen-bonding interactions between two adjacent sheets, the 2D layers are further stacked into the final 3D supramolecular structure. Compound 3is a 3D metal–organic framework (MOF), showing 1D helical channels. The progressive skeletal variation from the 1D chains (1) to 2D sheets (2) and 3D framework (3) is attributed to the flexibility of both the Ce(III) coordination sphere and coordination modes of the Hpydc–and pydc2–ligands under different reaction conditions. The three compounds illustrate how the tuning of the coordination geometry of Ce(III) translates into different dimensionality, which is readily influenced by reaction temperature and ancillary ligand presence. Moreover, the porosity of MOF 3was confirmed by N2and CO2gas adsorption/desorption. Finally, the catalytic activity of MOF 3was examined in acetalization reactions in a series of aromatic aldehydes with methanol.

A new Zn(II)-based coordination polymer (CP) having the formula [Zn(L)(2,2′-bpy)] (1) was synthesized using ZnCl2, 3,3′-(anthracene-9,10-diyl)diacrylic acid ligand (H2L), and 2,2′-bipyridine (2,2′-bpy) in DMF under solvothermal conditions. Here, the anthracene-based dicarboxylic acid ligand shows aggregation-induced emission (AIE) activity in an ethanol/hexane medium. Single-crystal X-diffraction analysis reveals that the one-dimensional (1D) zigzag chainlike structure of 1is assembled from tetrahedrally coordinated Zn2+ions interconnected by 2,2′-bpy and ditopic anthracene-based ligand molecules. The crystal structure analysis reveals that the ditopic anthracene-based flexible ligand adopts a twisted conformation in the CP crystal compared to its free state. Because of the twisted conformation of the AIE active ligand in the CP crystal, a large (∼80 nm) hypsochromic shift was observed in the emission spectrum with a drastic color change compared to the free state of ligand. The origin of these rare fluorescence properties is ascribed to the twisted diacrylic acid ligand conformation and rigidity in the CP crystal. An unprecedented response was observed toward singlet oxygen (1O2) by 1via a fluorescence turn-off mechanism. The presence of the anthracene moiety is the main influential factor for 1O2sensing, which undergoes [4 + 2] cycloaddition reaction with 1O2, producing a nonemissive 9,10-endoperoxide product. The unique photoluminescence properties along with tunable fluorescence responses indicate that incorporating an AIE active anthracene core into the CP crystal is a beneficial strategy to develop new fluorescent materials with significant sensing ability.

Trypanosoma cruziis the causative pathogen of Chagas disease and the main culprit for cardiac-related mortality in Latin-America triggered by an infective agent. Incapable of synthesizing purines de novo, this parasite depends on acquisition and processing of host-derived purines, making purine (nucleoside) analogues a potential source of antitrypanosomal agents. In this respect, hitherto 7-deazaadenosine (tubercidin) analogues attracted most attention. Here, we investigated analogues with an additional nitrogen (N1) removed. Structure–activity relationship investigation showed that C7 modification afforded analogues with potent antitrypanosomal activity. Halogens and small, linear carbon-based substituents were preferred. Compound 11proved most potent in vitro, showed full suppression of parasitemia in a mouse model of acute infection, and elicited 100% animal survival after oral dosing at 25 mg/kg b.i.d. for 5 and 15 days. Cyclophosphamide-induced immunosuppression led to recrudescence. Washout experiments demonstrated a lack of complete clearance of infected cell cultures, potentially explaining the in vivo results.

Low-dimensional lead halide hybrid perovskites are nowadays in the spotlight because of their improved stability and extensive chemical flexibility compared to their 3D perovskite counterparts, the current challenge being to design functionalized organic cations. Here, we report on the synthesis and full characterization of a perovskite-like hybrid (a perovskitoid) where the 1D lead iodide layout is patterned with a donor–acceptor charge transfer complex (CTC) between pyrene and tetracyanoquinodimethane, with a chemical formula of (C20H17NH3)PbI3·(C12H4N4). By combining multiple structural analysis and spectroscopic techniques with ab initio modeling, we show that the electronic, optical, and charge-transport properties of the hybrid materials are dominated by the organic CTC, with the inorganic backbone primarily acting as a template for the organization of the donor and acceptor molecules. Interestingly, time-resolved microwave conductivity (TRMC) measurements show an enhanced photocurrent generation in the 1D hybrid compared to the pure organic charge-transfer salt, likely associated with transient localization of the holes on the lead-iodide octahedra. This observation is in line with the close energy resonance between the valence crystal orbitals of the lead-iodide lattice and the frontier occupied molecular orbitals of pyrene predicted by the DFT calculations. Therefore, it paves the way toward the design of new hybrid low-dimensionality perovskites offering a synergic combination of organic and inorganic functionalities.

Synthetic studies toward the ent-kauranoid family of diterpene natural products are reported. An intramolecular (4 + 3) cycloaddition allows the direct elaboration of diverse natural product frameworks, encompassing a challenging bicyclo[3.2.1]octane core. The established routes comprise only a few synthetic operations (3–5 steps), transforming a range of simple starting materials into the tetracyclic scaffolds that are commonly found in many ent-kaurene metabolites.

Cyclic imino ether heterocycles are used as ligands in transition metal catalysis, in various drugs and as reactive monomers in living cationic ring-opening polymerization (CROP). While five- and six-membered cyclic imino ethers, i.e. 2-oxazolines and 4,5-dihydro-1,3-oxazines, have extensively been studied in these areas, their seven-membered ring counterparts have remained unexplored. Herein, we report the synthesis of 2-phenyl-4,5,6,7-tetrahydro-1,3-oxazepine allowing reassignment of the earlier, incorrectly reported 4,5,6,7-tetrahydro-1,3-oxazepines as their N-acylated pyrrolidine isomers. Finally, we also report a comparison of the CROP reactivity of a homologous series of cyclic imino ethers with a 2-carbon, 3-carbon, and 4-carbon methylene bridge, revealing a remarkable ring size effect.

Fast and scalable low-temperature deposition of microscale metallic features is of utmost importance for the development of future flexible smart applications including sensors, wireless communication, and wearables. Recently, a new class of metal–organic decomposition (MOD) copper inks was developed, consisting of self-reducing copper formate containing amine complexes. From these novel inks, copper metal features with outstanding electrical conductivity (±105S cm–1) are deposited at a temperature of 150 °C or less, which is well below the reduction temperature of orthorhombic α-copper formate (around 225 °C). However, the underlying principle of this reaction mechanism and the relationship between the corresponding temperature shift and the amine coordination are still under debate. The current study provides a full explanation for the shift in reduction temperatures via in situ characterization. The results clearly indicate that the structural resemblance and stability of the Cu(II) starting compound and the occurring Cu(I) intermediate during the in situ reduction are the two main variables that rationalize the temperature shift. As such, the thermal compatibility of copper MOD inks with conventional plastic substrates such as polyethylene terephthalate can be explained, based on metal–organic complex properties.

The structure of a γ-hydroxyphosphine oxide derivative [(4‑hydroxy‑2-methylpentan-2-yl)diphenylphosphine oxide, C18H23O2P (1)], was studied by using various spectroscopic tools including IR, NMR (1H, 31P, 13C) spectroscopy and the mass spectrometry and single crystal X-ray diffraction. The title compound was found to crystallize in three different ways, depending on the absolute configuration at the C2 carbon (R, Sor racemate). The Hirshfeld surface, curvedness, shape index and 2D-fingerprint plots of the title compound were used to evaluate various intermolecular interactions within the crystal structure. The theoretically optimized geometry has been computed using density functional theory (DFT) calculations, and HOMO-LUMO analyses have been carried out.

Chagas disease is the leading cause of cardiac-related mortality in Latin American countries where it is endemic. Trypanosoma cruzi, the disease-causing pathogen, is unable to synthesize purines de novo, necessitating salvage of preformed host purines. Therefore, purine and purine-nucleoside analogues might constitute an attractive source for identifying antitrypanosomal hits. In this study, structural elements of two purine-nucleoside analogues (i.e., cordycepin and a recently discovered 7-substituted 7-deazaadenosine) led to the identification of novel nucleoside analogues with potent in vitro activity. The structure–activity relationships of substituents at C-7 were investigated, ultimately leading to the selection of compound 5, with a C-7 para-chlorophenyl group, for in vivo evaluation. This derivative showed complete suppression of T. cruziY-strain blood parasitemia when orally administered twice daily for 5 days at 25 mg/kg and was able to protect infected mice from parasite-induced mortality. However, sterile cure by immunosuppression could not be demonstrated.

A gold-catalyzed post-Ugi ipso-cyclization for the diastereoselective synthesis of spirocyclic pyrrol-2-one-dienone system is described. Tuning the catalytic system, solvent, and temperature allowed selectively attaining two sets of diastereoisomers. The scope of the process has been evaluated, and a putative mechanistic model was proposed.

Synthesis of 2D MOFs is often sensitive to the reaction conditions like temperature and solvent etc.Cu(ii)-5-azidoisophthalate MOF (Cu(ii)–5N3IP) has been synthesized at room temperature as well as under solvothermal conditions. The azide functional group remained stable during solvothermal synthesis at 85 °C. Cu(ii)–5N3IP crystallized in a Kagomé-type structure. Typical Cu2paddle-wheels are connected to each other by 5N3IP ligands in infinite 2D sheets in the (001) plane, featuring 1D infinite channels within each layer. This MOF is used for the adsorption of methylene blue (MB), rhodamine B (RhB), methyl orange (MO), and Congo red (CR). The adsorption is selective to the dimensions, shapes and ionic strengths of the dyes. Cu(ii)–5N3IP exhibited adsorption rates in the order MB > CR > RhB > MO. Cu(ii)–5N3IP is used as a catalyst for aerobic oxidation and Knoevenagel condensation. 3–10 mol% of Cu–5N3IP selectively catalyzes the oxidation of benzyl alcohol to benzaldehyde in 9–20 h at 60 °C. In Knoevenagel condensation, the reaction of both unsubstituted and substituted benzaldehydes at room temperature was observed at a very low catalyst loading of 3 mol% of MOF within a short time of 3–60 min. This 2D MOF has proved to be more efficient for dye adsorption and the catalytic applications under investigation (such as alcohol oxidation and Knoevenagel condensation) than its analogous 3D or 0D materials.

A rare case of low-percentage trivalent lanthanide doping in multinuclear lanthanide polyoxometalates (LnPOMs) was investigated. The [La4(MoO4)(H2O)16(Mo7O24)4]14–polyanion was chosen as the host material for this study. In this polyanion the central [La4(MoO4)]10+core is coordinated by four heptamolybdate groups as well as 16 water molecules. The tetranuclear lanthanum POM was doped with 5% of Eu3+, Tb3+, Sm3+, Dy3+, Nd3+, Er3+, and Yb3+(according to synthesis), and the structures and luminescence properties of the x%Ln:LaPOMs were investigated. Additionally a series of tetranuclear lanthanide POMs built from [Mo7O24]6–heptamolybdate polyanions with Eu3+, Tb3+, Sm3+, Dy3+, and Nd3+instead of La3+were synthesized, and a detailed analysis revealed that the tetranuclear clusters formed monomers or dimers linked through oxygen bridges. The smaller lanthanide ions, namely, Er3+and Yb3+, did not form tetranuclear clusters, but instead mononuclear sandwich-type POMs were obtained. The obtained structures were shown to be lanthanide-specific, and not a result of different synthetic/crystallization conditions. The luminescence properties of the x%Ln:LaPOMs were compared with the luminescence properties of the LnPOMs.

In this study, we present for the first time the immobilization of phosphotungstic acid (H3PW12O40, HPW) into the nanocages of a dual amino-functionalized ionic liquid (DAIL)-modified MIL-101(Cr) framework under mild conditions. The obtained PW/DAIL/MIL-101(Cr) was evaluated as a catalyst in the oxidation of benzyl alcohol using TBHP in chloroform. In order to obtain insights into the role of the DAIL during catalysis, a DAIL-free catalyst (HPW/MIL-101(Cr)) was also prepared. Both catalysts were fully characterized using several techniques. In comparison with the HPW/MIL-101(Cr) material, PW/DAIL/MIL-101(Cr) showed an enhanced catalytic performance in the selective oxidation of benzyl alcohol. This was mainly attributed to the ability of the DAIL groups to form hydrogen bonds, thus enhancing the accessibility of TBHP. Furthermore, the immobilization of the DAIL groups onto MIL-101(Cr) resulted in increased thermal stability of the obtained PW/DAIL/MIL-101(Cr) which showed stability up to 400 °C. Moreover, the PW/DAIL/MIL-101(Cr) catalyst exhibited good recyclability and selectivity. The catalyst could be reused for at least five cycles with no significant leaching of the tungsten species or loss of crystallinity and activity.

A stereoselective dearomative cyclopentannulation of benzofurans is reported. A previously reported dearomative (3 + 2) cycloaddition of indoles with 1,4-dithiane-fused allyl cations was found to lack stereoselectivity when more substituted cyclopentene rings are targeted. However, for benzofuran substrates, excellent levels of stereoselectivity were observed for the same allyl cation reagents under very similar reaction conditions. In this full account, we provide a mechanistic rationale and some design principles that govern the stereoselectivity of the intriguing dearomative transformations using dithioallyl cations and demonstrate how the stereoselectivity depends on electronic factors of the starting materials. The stereoselective methodology is also applied in a straightforward dearomative synthesis of the tricyclic sesquiterpenoid natural product aplysin and its analogues, starting from a simple benzofuran.

3‐Methylene‐4‐(trifluoromethyl)azetidin‐2‐ones were efficiently prepared from the corresponding 3‐oxo‐4‐trifluoromethyl‐β‐lactams and successfully evaluated as novel building blocks in organic synthesis. In particular, Michael additions, electrophilic additions, and cycloadditions were applied to allow easy access to a broad variety of stereodefined mono‐ and spirocyclic 4‐CF3‐β‐lactams as useful synthetic intermediates en routeto a variety of biologically relevant CF3‐functionalized target structures. 3‐Methylene‐4‐(trifluoromethyl)azetidin‐2‐oneswere efficiently prepared from the corresponding 3‐oxo‐4‐trifluoromethyl‐β‐lactams. Michael additions, electrophilic additions, and cycloadditions were applied to allow easy access to a broad variety of stereodefined mono‐ and spirocyclic 4‐CF3‐β‐lactams as useful synthetic intermediates en routeto a variety of biologically relevant CF3‐functionalized target structures.

We report on the synthesis and characterization of a second generation of ruthenium catalysts bearing different sized indenylidene ligands, denoted as RuCl2(3-(2,6-xylyl)-1-indenylidene)(SIMes)(PCy3) 5a, RuCl2(4-methyl-3-(o-tolyl)-1-indenylidene)(SIMes)(PCy3) 5b, RuCl2(3-1-naphthyl-1-indenylidene)(SIMes)(PCy3) 5cand RuCl2(3-(p-fluorophenyl)-1-indenylidene)(SIMes)(PCy3) 5d. These complexes were characterized by NMR, IR, HRMS and elemental analysis. Moreover, the configurations of complexes 5a, 5band 5dwere confirmed by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 5a–dwere evaluated in several olefin metathesis reactions: the RCM of substrates 6and 7, the RCEYM of substrate 8and the ROMP of COD, in comparison with commercially available catalyst 3a. Careful analysis of the catalytic performances and single-crystal X-ray diffraction data of complexes 5a–5dreveal that the steric modification on the 3-phenyl group has a significant influence on the ligand congestion around the ruthenium center, altering the catalytic activity in metathesis reactions. In addition, the better-performing complex 5awas further investigated in the RCM of substrate 6in comparison with complex 3cand benchmark complexes 1b, 2and 3a.

Novel microwave‐assisted syntheses of pyrazino[2,1‐b]quinazolines and 3‐indolyl‐2(1H)‐pyrazinones employing silver(I)‐ or gold(I)‐catalyzed protocols have been elaborated. The scope and limitations of these processes have been investigated.

Homothiacalix[n]arenes have been largely underexposed compared with related (homo)heteracalixarenes, although their inherent structural features are particularly attractive for supramolecular host–guest chemistry. In this contribution, the synthetic macrocyclization protocols that afford homothiacalix[n]arenes have been reinvestigated and optimized, providing straightforward access to the parent homothiacalix[4]arene skeleton. Moreover, inner‐rim (bis and tetrakis) ester functionalization and dimethylenethia bridge oxidation were successfully performed as well. Solution‐phase (variable‐temperature) NMR spectroscopy studies and solid‐state X‐ray structures provided complementary information on the conformational features of the novel macrocycles.

New metal‐containing ionic liquids [Cu(CH3CN)n][Tf2N] (n=2, 4; Tf2N=bis(trifluoromethylsulfonyl)‐ amide) have been synthesised and used as a non‐aqueous electrolyte for the electrodeposition of copper at current densities greater than 25 A dm−2. The tetrahedral copper(I)‐containing cation in [Cu(CH3CN)4][Tf2N] is structurally analogous to quaternary ammonium and phosphonium ionic liquids and overcomes problems of metal solubility and mass transport. Two CH3CN ligands are removed at elevated temperatures to give [Cu(CH3CN)2][Tf2N], which can be used as a concentrated non‐aqueous electrolyte. The structural and electrochemical characterisation of these compounds is described herein.

In this contribution the first examples of so‐called rigid‐core, T‐shaped imidazolium ionic liquid crystals, in which the C‐2 atom of the imidazolium ring is substituted with an aryl moiety decorated with one or two alkoxy chains, are described. The length of the alkoxy chain(s) was varied from six to eighteen carbon atoms (n=6, 10, 14–18). Whereas the compounds with one long alkoxy chain display only smectic A phases, the salts containing two alkoxy chains exhibit smectic A, multicontinuous cubic, as well as hexagonal columnar phases, as evidenced by polarising optical microscopy, differential scanning calorimetry, and powder X‐ray diffraction. Structural models are proposed for the self‐assembly of the molecules within the mesophases. The imidazolium head groups and the iodide counterions were found to adopt a peculiar orientation in the central part of the columns of the hexagonal columnar phases. The enantiotropic cubic phase shown by the 1,3‐dimethyl‐2‐[3,4‐bis(pentadecyloxy)phenyl]imidazolium iodide salt has a multicontinuous Pm$\bar 3$mstructure. To the best of our knowledge, this is the first example of a thermotropic cubic mesophase of this symmetry.

The regio‐ and stereoselective construction of the azocino[cd]indole core was achieved by applying a Pd‐catalyzed intramolecular acetylene hydroarylation protocol. The applicability of a similar strategy for the synthesis of the azepino[b]indole framework is demonstrated.

A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C1C1CNPyr)2(Tf2N)4] and [Co(C1C2CNPyr)6][Tf2N]8, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids.

A mild, efficient and stable copper iodide nanoparticle (CuI NP)‐catalyzed regioselective synthesis of 3‐nitro‐2‐arylimidazo[1,2‐a]pyridines was developed. Substituted 2‐amino pyridines successfully reacted with both electron‐rich and electron‐deficient β‐nitro styrenes to produce the desired products in good to excellent yields. Hot filtration tests confirmed the heterogeneous nature of the CuI NPs. The nanocatalyst showed good reusability up to three consecutive cycles without any significant loss in its activity and product yield, confirmed by high‐resolution transmission electron microscopy (HR‐TEM) analysis. Use of molecular oxygen as oxidant is advantageous from an economic and environmental point of view. A copper iodide nanoparticle‐catalyzedsynthesis of 3‐nitro‐2‐arylimidazo[1,2‐a]pyridines has been developed under oxygen atmosphere. The reaction exhibited a high level of regioselectivity with moderate to excellent yield.

Photoluminescent molecular crystals integrated with the ability to transform light energy into macroscopic mechanical motions are a promising choice of materials for both actuating and photonic devices. However, such dynamic photomechanical effects, based on molecular organoboron compounds as well as phosphorescent crystalline materials, are not yet known. Here we present an intriguing example of photomechanical molecular single crystals of a newly synthesized organoboron containing Lewis acid–base molecular adduct (BN1, substituted triphenylboroxine and 1,2-di(4-pyridyl)ethylene) having a capsule shape molecular geometry. The single crystals of BN1 under UV light exhibit controllable rapid bending–shape recovery, delamination, violent splitting–jumping, and expanding features. The detailed structural investigation by single-crystal X-ray diffraction and 1H NMR spectroscopy reveals that the photosalient behavior of the BN1 single crystals is driven by a crystal-to-crystal [2 + 2] cycloaddition reaction, supported by four donor–acceptor type B←N bonds. The instant photomechanical reaction in the BN1 crystals occurs under UV on account of sudden release of stress associated with the strained molecular geometry, significant solid-state molecular movements (supramolecular change), and cleavage of half intermolecular B←N linkages to result in a complete photodimerized single-crystalline product via the existence of two other intermediate photoproducts. In addition, the BN1 crystals display short-lived room temperature phosphorescence, and the photodynamic events are accompanied by the enhancement of their phosphorescence intensity to yield the photoproduct. Interestingly, the molecular crystals of the final photoproduct polymerize at ambient conditions when recrystallized from the solution forming a 2D supramolecular crystalline polymer stabilized by the retention of all B←N coordination modes.

The dissolution process of metal complexes in ionic liquids was investigated by a multiple‐technique approach to reveal the solvate species of the metal in solution. The task‐specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare‐earth elements. The crystal structures of the compounds [Eu2(bet)8(H2O)4][Tf2N]6, [Eu2(bet)8(H2O)2][Tf2N]6⋅2H2O, and [Y2(bet)6(H2O)4][Tf2N]6were found to consist of dimers. These rare‐earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C4mim][Tf2N] (C4mim=1‐butyl‐3‐methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, 1H, 13C, and 89Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X‐ray absorption fine structure) and HEXS (high‐energy X‐ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

N‐Alkyl‐N‐methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium‐containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2‐ thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group CnH2n+1was varied from eight to twenty carbon atoms (n=8, 10–20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X‐ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self‐assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium‐containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium‐containing compound shows intense red photoluminescence with high colour purity.

Water-soluble, stable, and easily synthesizable 1:4 complexes of rare-earth ions with 8-hydroxy-5-nitroquinolinate ligands have been prepared. These complexes can be sensitized by visible light with wavelengths up to 480 nm and show near-infrared emission in aqueous solution. The incorporation of a nitro group in the quinoline moiety shifts its absorption bands to longer wavelengths and also increases its molar absorptivity by a factor of 2.5, thereby significantly enhancing its light-harvesting power. The presence of the nitro group also increases the solubility of the resulting complexes, making them water-soluble. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Functionalized oxacalixmarenenpyrimidines have been synthesized by SNAr on 4,6-dihalopyrimidine building blocks. Depending on the SNAr conditions, either a mixture of oxacalixnarenes, ranging from oxacalix4- up to oxacalix12arene, could be prepared or the oxacalix4arene could be synthesized selectively in a high yield. The electrophilic (pyrimidine) and the nucleophilic components could both be varied, allowing the preparation of functionalized oxacalix4arenes. Moreover, the procedure also gives access to the analogous thiacalix4arenes.

Lanthanide-containing liquid crystals exhibiting a mesophase close to room temperature were obtained by adduct formation between a long-chain salicylaldimine Schiff base and tris(2-thenoyltrifluoroacetonato)lanthanide(III) complexes or tris(benzoyltrifluoroacetonato)lanthanide(III) complexes. The mesophase was identified as a smectic A phase. The temperature range of the mesophase was found to decrease over the lanthanide series, and no mesophase was observed for the complexes of the smallest lanthanide ions. The photoluminescence of the europium(III), samarium(III), neodymium(III), and erbium(III) complexes was studied. It is shown that the clearing point can be detected by monitoring the luminescence decay time as a function of the temperature.

The alkali-metal salts of meta-substituted benzoic acids exhibit a smectic A mesophase at high temperatures. These compounds are examples of liquid crystals without terminal alkyl chains. The influence of the metal ion and of the type of substituents on the transition temperatures is discussed. Compounds with the substituent in the ortho- and para-positions are non-mesomorphic. The crystal structures of the compounds Rb(C7H4ClO2)(C7H4ClO2H), Na(C7H4IO2)(H2O), K(C7H4ClO2)(C7H4ClO2H) and Rb(C7H4BrO2)(C7H4BrO2H) have been determined by X-ray crystallography. These compounds possess a layerlike structure in the solid state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Lanthanide(III) complexes of p-nitrobenzenesulfonic acid, Ln(p-NBSA)3, m-nitrobenzenesulfonic acid, Ln(m-NBSA)3, and 2,4-nitrobenzenesulfonic acid, Ln(2,4-NBSA)3, were prepared, characterized and examined as catalyst for the nitration of benzene, toluene, xylenes, naphthalene, bromobenzene and chlorobenzene. The initial screening of the catalysts showed that lanthanum(III) complexes were more effective than the corresponding ytterbium(III) complexes, and that catalysts containing the bulky 2,4-NBSA ligand were less effective than the catalyst containing p-NBSA (nosylate) or m-NBSA ligands. Examination of a series of Ln(p-NBSA)3 and Ln(m-NBSA)3 catalysts revealed that there is a clear correlation between the ionic radii of the lanthanide(III) ions and the yields of nitration, with the lighter lanthanides being more effective. The X-ray single crystal structure of Yb(m-NBSA)3·6H2O shows that two m-NBSA ligands are directly bound to the metal centre while the third ligand is not located in the first coordination sphere, but it is hydrogen bonded to one of the water molecules which is coordinated to ytterbium(III). NMR studies suggest that this structure is preserved under the conditions used in the nitration reaction. The structure of Yb(m-NBSA)3 is markedly different from the structure of the well-known ytterbium(III) triflate catalyst. The coordination of the nitrobenzenesulfonate counterion to the lanthanide(III) ion suggests that steric effects might play an important role in determining the efficiency of these novel nitration catalysts. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)