Stradivari's Varnish Revisited: Feature Improvements Using Chemical Modification.

The most widespread varnish formulations used by master violin-makers of the "Italian Golden Age", including Antonio Stradivari, were based on mixtures of siccative oils (e.g., linseed oil) and natural resins (e.g., colophony). Similar formulations are still used for the finish of contemporary instruments. Although most precious violins made by Stradivari and other Cremonese Masters are kept in museums, several instruments are still played and their finish may undergo deterioration due to contact with the players. Moreover, the decay of the traditional varnish may occur due to mechanical stress and natural aging caused by environmental agents (e.g., exposure to uncontrolled light, humidity, and temperature changes). The main aim of this research work is to investigate the possible improvement of varnish resistance to the decay induced by different aging processes. For this purpose, the traditional varnish (linseed oil/colophony 3:1 w/w) was recreated in the laboratory following an ancient recipe and then it was functionalized with a cross-linking agent (3-Glycidyloxypropyltrimethoxysilane, GLYMO). Plain and functionalized varnishes underwent artificial aging (UV light, temperature, and humidity variations), and their properties were comparatively studied using different techniques. All the results suggest that the functionalized varnish displays improved resistance to the aging process and particularly enhanced photostability and increased hardness (resistance to scratches).

Electrochemically Driven Swinging of a Nitrobenzyl Pendant Arm in a Nickel Scorpionand Complex.

A radical anion -NO2 .- is formed upon an electrochemically reversible one-electron reduction of the square-planar NiII complex of N-nitrobenzylcyclam. The -NO2 .- group goes to occupy an axial position of the metal ion, thus establishing a significant electronic interaction with the metal center. In particular, the ESR spectrum supports the occurrence of an electron transfer from -NO2 .- to the metal, which therefore presents a significant NiI character. On re-oxidation, the nitrobenzyl side chain detaches and the NiII complex is restored, providing an example of a fully reversible redox driven intramolecular motion.

Fluorogenic Detection of Sulfite in Water by Using Copper(II) Azacyclam Complexes.

Copper(II) azacyclam complexes (azacyclam = 1,3,5,8,12-pentaazacyclotetradecane) containing naphthyl or dansyl subunits can be prepared by template synthesis involving proper sulfonamide derivatives as locking fragments. The macrocyclic complexes are very poorly emissive due to the fluorescence-quenching behavior displayed by Cu2+ ions. However, the fluorescence can be recovered as a result of the decomposition of the complexes, which induces the release of free light-emitting subunits to the solution. This reaction takes place very slowly in neutral water but its rate is increased by the presence of sulfite. Therefore, [Cu(azacyclam)]2+ derivatives have been investigated as simple chemical probes for the fluorogenic detection of sulfite both on laboratory and real samples. Preliminary tests performed on samples of white wine provided sulfite concentration values that are in agreement with those obtained by a standard analytical method.

Preliminary Cleaning Approach with Alginate and Konjac Glucomannan Polysaccharide Gel for the Surfaces of East Asian and Western String Musical Instruments.

The cleaning of string musical instruments is challenging due to the traditional finishing treatments used by the makers. Multilayered coating systems were applied to Western musical instruments, while the Nakdong technique was applied in East Asia. Furthermore, by restorations and performance, dust and grime were overlapped together with polishes, adhesives, and varnishes. Gel cleaning is important in the field of conservation because of the ability to selectively remove chemical and biological degradation products from the surface, minimizing the interactions with the inner layers. In this study, hydrogels based on sodium alginate (SA) and konjac glucomannan (KG) polysaccharides were applied on laboratory mock-ups of East Asian and Western instruments to test their ability to remove synthetic soiling and sweat from the surface. In particular, SA cross-linked with calcium cations and KG cross-linked with borate gels were used. To control the exposure of the cleaning solvent on the surface of mock-ups, the moisture content of the gels was determined. The effectiveness of removing synthetic contaminants was investigated by noninvasive analytical methods. Stereomicroscopy and colorimetry, together with Fourier Transform Infrared (FTIR) spectroscopy in reflection mode and X-Ray Fluorescence (XRF), were used to evaluate the cleaning efficacy. Overall, polysaccharide hydrogels resulted in promising cleaning systems on both smooth and rough surfaces of wood.

Biopolymer Gels as a Cleaning System for Differently Featured Wooden Surfaces.

The cleaning of some wooden artefacts can be challenging due to peculiar surface roughness and/or particular finishing treatments that favour the deposition of dirt and contaminants. The most common cleaning system used by conservators is agar gel, characterized by its rigidity and brittleness, which challenges the cleaning of rough and irregular surfaces typical of most wooden artefacts. In this work, alginate crosslinked with calcium (CA) and konjac glucomannan crosslinked with borax (KGB) gels were proposed to solve this issue. They were prepared and applied to smooth- and rough-surfaced mock-ups replicating wooden musical instruments' surfaces that had been subsequently covered by artificial soiling and sweat contaminants. The mechanical properties of CA and KGB gels, including their stability over a 60-day storage time, were evaluated by a texture analyzer, while cleaning efficacy was analytically evaluated by non-invasive X-ray fluorescence mapping and profilometric investigation. CA gel appeared to have a higher tensile strength and elongation at break. KGB gel was shown to be soft and resilient, indicating its suitability for cleaning rough surfaces. After repeating the cleaning application three times on the rough-surfaced mock-ups, both the CA and KGB gels were shown to have cleaning efficacy. The results obtained with CA and KGB were compared with those from the Agar application.

A Nanoprobe Based on Gated Mesoporous Silica Nanoparticles for The Selective and Sensitive Detection of Benzene Metabolite t,t-Muconic Acid in Urine.

Benzene is a highly toxic aromatic hydrocarbon. Inhaling benzene can cause dizziness, vertigo, headaches, aplasia, mutations and, in the most extreme cases, cancer. Trans,trans-muconic acid (t,t-MA) is one of the metabolization products of benzene. Although different analytical methods have been reported for the determination of t,t-MA, these are often expensive, require trained personnel, are not suitable for on-site measurements, and use hazardous organic solvents. For these reasons, the development of reliable, selective and sensitive methods for rapid and in situ detection of t,t-MA are of importance. Addressing this challenge, a nanodevice for the selective and sensitive quantification of t,t-MA in urine is reported. The nanodevice used is achieved using mesoporous silica nanoparticles loaded with a dye reporter and capped with a dicopper(II) azacryptand. Pore opening and payload release is induced rapidly (10 min) and selectively with t,t-MA in urine, using a simple fluorimeter without sample pretreatment.

Reflection FTIR spectroscopy for the study of historical bowed string instruments: Invasive and non-invasive approaches.

A micro-sample detached from a historical bowed string instrument represents a valuable record of the materials used by the great Masters of violin-making art. It allows researchers to collect a wealth of information and to disclose - at least partially - their procedures for finishing and varnishing. In the present work, a set of four cross-sectioned micro-samples - collected from well-preserved bowed string instruments made by Antonio Stradivari and Lorenzo Storioni - are investigated by Synchrotron Radiation (SR) FTIR micro-spectroscopy in reflection mode. SR-FTIR spectra are discussed both as point analysis and as univariate and multivariate chemical maps. The same cross-sections are also investigated by optical microscopy under UV light and SEM-EDX. Moreover, data obtained directly from the musical instruments by a non-invasive approach employing a portable reflection FTIR spectrometer are also considered. FTIR investigation of the cross-sections is a challenging task for such brittle and complex layered micro-samples. Nevertheless, the high intensity of the analytical SR beam used in reflection geometry allowed us to obtain informative FTIR spectra and to fully preserve the integrity of the samples. Both the non-invasive and the micro-invasive reflection FTIR approaches can reveal the materials spread on the wood surface to finish the musical instruments. The fingerprint of Lorenzo Storioni's production around 1790 emerged from the study of the cross-sectioned samples, definitely different from the technique of Stradivari.

Detection of Copper(II) in Water by Methylene Blue Derivatives.

Two novel phenothiazin-5-ium derivatives bearing cyclam moieties (3 a+ and 3 b+ ) were synthesized and investigated as Cu2+ sensors. Both ligands show intense spectral changes in the presence of Cu2+ in aqueous solutions. The high molar extinction coefficient of the chromophore allows both naked eye detection and spectrophotometric quantitative determination of the cation at a micromolar-concentration scale. 3 a+ was found to outperform 3 b+ , showing negligible spectral changes in the presence of excesses of other metal cations.

Polyamine-Based Organo-Clays for Polluted Water Treatment: Effect of Polyamine Structure and Content.

Hybrid materials based on clays and polyamines are supposed to be efficient heavy metals sorbents due to the well-known adsorption behaviour of the clay matrix and to the coordination properties of un-protonated amino groups. For this purpose, a montmorillonite clay was modified with three different aliphatic polyamines: L6 and L10 have a linear structure with six and ten amino groups, respectively, while B14 is a branched polyamine with fourteen amino groups. Initial amine concentration was the main parameter investigated and data were fitted with Langmuir and Freundlich models. Interaction mechanisms between clay and amines were deeply investigated by different experimental techniques such as X-ray powder diffraction (XRD), thermal analysis measurements (DTG), Fourier Transform Infrared Spectroscopy (FT-IR) and diffuse reflectance (NIR) spectroscopy. Experimental results showed that the amount of amines efficiently immobilized in the solid phase can be increased by increasing the initial concentration of polyamines in the clay modification process. These data were best fitted by Freundlich model, indicating a presence of surface sites of different nature. In the resulting hybrid materials, neither the accessibility of the NH/NH2 groups of the amines, nor the accessibility of the structural OH of the clay was hindered. Several preliminary tests in La ions' uptake and release from aqueous solution were also carried out. In the conditions used for this study, total metal ion removal was achieved at sufficiently low linear amine loadings (i.e., 0.45 mmol/gclay for the small L6 amine), suggesting that these hybrid materials are promising for the proposed application in environmental remediation.

Preparation and characterization of photocatalytic Gd-doped TiO2 nanoparticles for water treatment.

In recent years, the photocatalytic process by using TiO2 nanoparticles (NPs) has produced a great interest in wastewater treatment due to its interesting features such as low-cost, environmental compatibility, and especially capacity to eliminate persistent organic compounds as well as microorganisms in water. In the present work, the photocatalytic activity of Gd-doped TiO2 nanopowders, with different doping amount 0.1, 1, and 5 mol% synthesized by the sol-gel method, was studied under UV/Visible irradiation for water treatment application. The Gd-doped TiO2 nanoparticles were investigated for their photocatalytic degradation of methylene blue (MB) dye and antibacterial activities against two bacterial strains namely Stenotrophomonas maltophilia (S. maltophilia) and Micrococcus luteus (M. luteus). MB dye was used as a pollutant model to estimate reactive oxygen species (ROS) generation and to correlate killing action of nanoparticles with the generation of ROS. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and Raman spectroscopy were used to characterize the as-synthesized nanomaterials. Photocatalytic, as well as antibacterial tests, showed that doping with an appropriate amount of Gd could reduce the radiative recombination process of photogenerated electron-hole pairs in TiO2 and induce a significant enhancement in photocatalytic and consequently antibacterial activity. The experimental sequence of bactericidal activity and photocatalytic degradation efficiency exhibited by the different gadolinium-doped nanoparticles was the following: 0.1 mol% Gd-doped TiO2 > 1 mol% Gd-doped TiO2 > 5 mol% Gd-doped TiO2 > pure titania.

Mid and Near-Infrared Reflection Spectral Database of Natural Organic Materials in the Cultural Heritage Field.

This study presents mid and near-infrared (7500-375 cm-1) total reflection mode spectra of several natural organic materials used in artworks as binding media, consolidants, adhesives, or protective coatings. A novel approach to describe and interpret reflectance bands as well as calculated absorbance after Kramers-Kronig transformation (KKT) is proposed. Transflection mode spectra have represented a valuable support both to study the distorted reflectance bands and to validate the applicability and usefulness of the KK correction. The aim of this paper is to make available to scientists and conservators a comprehensive infrared reflection spectral database, together with its detailed interpretation, as a tool for the noninvasive identification of proteins, lipids, polysaccharides, and resins by means of portable noncontact FTIR spectrometers.

Anion Recognition in Water, Including Sulfate, by a Bicyclam Bimetallic Receptor: A Process Governed by the Enthalpy/Entropy Compensatory Relationship.

The dimetallic system [CuII2 (L)]4+ contains two facing equivalent metallocyclam subunits and incorporates ambidentate anions, mono- (halides) and poly-atomic (sulfate), which bridge the two CuII centres. Isothermal titration calorimetry (ITC) experiments in water showed that the log K values of the inclusion equilibria for halides and sulfate varied over a restricted interval (3.6±0.2), which indicated lack of selectivity and that similarity of ΔG° values resulted from the unbalanced contribution of the ΔH° and TΔS° terms: the more favourable the one, the less favourable the other. In particular, a linear dependence of ΔH° and TΔS° was observed (a typical enthalpy/entropy compensatory diagram), which assigned a major role to hydration terms: 1) a more hydrated anion resulted in a more endothermic dehydration process; and 2) a larger number of water molecules released to the solution resulted in a more positive TΔS°. Limiting cases refer to the complexation 1) of the poorly hydrated iodide (highly exothermic process, entropically disfavoured), and 2) of the highly hydrated sulfate (moderately endothermic process, entropically very favoured). Anion receptors operating in water belong to two main domains: 1) those exhibiting positive ΔH° and positive TΔS° (+/+ signature), and 2) those displaying the opposite behaviour: (-/- signature). The receptor investigated herein connects the two domains, along the ΔH°/TΔS° straight line, thanks to the hidden role of the versatile metal-anion interaction.

Bimacrocyclic Effect in Anion Recognition by a Copper(II) Bicyclam Complex.

The dicopper(II) complex of the bimacrocyclic ligand α,α'-bis(5,7-dimethyl-1,4,8,11-tetraazacyclotetradecan-6-yl)-o-xylene, 2, interacts with selected anions in dimethyl sulfoxide solution according to two different modes: (i) halides (Cl-, Br-, and I-) and N3 - coordinate the two metal centers at the same time between the two macrocyclic subunits that face each other and (ii) anionic species that do not fit the bridging coordination mode (e.g., NCO-, SCN-, CH3COO-, NO3 -, and H2PO4 -) interact with copper(II) ions only at the "external" positions or their interaction is too weak to be detected. Occurrence of the bridging interaction is demonstrated by X-ray crystallographic studies performed on the adduct formed by [Cu2(2)]4+ with azide and by electron paramagnetic resonance investigation, as the anion coordination between the two copper(II) centers induces spin-spin coupling. Isothermal titration calorimetry experiments performed on [Cu2(2)]4+ and, for comparison, on [(5,7-dimethyl-6-benzyl-1,4,8,11-tetraazacyclotetradecane)copper(II)], representing the mononuclear analogue, allowed determination of thermodynamic parameters (log K, ΔH, and TΔS) associated with the considered complex/anion equilibria. Thermodynamic data showed that adducts formed by [Cu2(2)]4+ with halides and azide benefit from an extra stability that can be explained on the basis of the anion advantage of simultaneously binding the two metal centers, i.e., in terms of the bimacrocyclic effect.

Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide.

The development of easy and affordable methods for the detection of cyanide is of great significance due to the high toxicity of this anion and the potential risks associated with its pollution. Herein, optical detection of cyanide in water has been achieved by using a hybrid organic-inorganic nanomaterial. Mesoporous silica nanoparticles were loaded with [Ru(bipy)3 ]2+ , functionalized with macrocyclic nickel(II) complex subunits, and capped with a sterically hindering anion (hexametaphosphate). Cyanide selectively induces demetallation of nickel(II) complexes and the removal of capping anions from the silica surface, allowing the release of the dye and the consequent increase in fluorescence intensity. The response of the capped nanoparticles in aqueous solution is highly selective and sensitive towards cyanide with a limit of detection of 2 µm.

Spectroscopic Analysis to Characterize Finishing Treatments of Ancient Bowed String Instruments.

Historical bowed string instruments exhibit acoustic features and aesthetic appeal that are still considered inimitable. These characteristics seem to be in large part determined by the materials used in the ground and varnishing treatments after the assembly of the instrument. These finishing processes were kept secret by the violinmakers and the traditional methods were handed down orally from master craftsmen to apprentices. Today, the methods of the past can represent a secret to be revealed through scientific investigations. The "Cremonese" methods used in the 17th and 18th centuries were lost as the last Great Masters from the Amati, Guarneri, and Stradivari families passed away. In this study, we had the chance of combining noninvasive and microinvasive techniques on six fragments of historical musical instruments. The fragments were detached from different instruments during extraordinary maintenance and restoration treatments, which involved the substitution of severely damaged structural parts like top plates, back plates, or ribs. Therefore, the fragments can offer to the scientists a valuable overview on the materials and techniques used by the violinmakers. The results obtained by portable X-ray fluorescence, optical microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and Fourier transform infrared microscopy allowed us to: (1) determine the stratigraphy of six instruments; (2) obtain new information about the materials involved in the finishing processes employed in Cremona; and (3) elucidate the technological relationship among the procedures adopted in the violin making workshops during the considered period.

Anions as Triggers in Controlled Release Protocols from Mesoporous Silica Nanoparticles Functionalized with Macrocyclic Copper(II) Complexes.

Three different mesoporous silica nano-sized materials (SC1, SC2, and SC3), loaded with [Ru(bipy)3 ]2+ dye (bipy=bipyridine) and functionalized on the external surface with three macrocyclic copper(II) complexes (C1, C2, and C3), were synthesized and characterized. When SC1, SC2, and SC3 were suspended in water, the entrapped [Ru(bipy)3 ]2+ dye was free to diffuse from the inner pores to the solution. However, addition of anions induced certain degrees of pore blockage, with subsequent dye release inhibition. Small monovalent and divalent anions were unable to induce complete pore blockage, whereas bulky and highly charged anions induced marked reductions in [Ru(bipy)3 ]2+ delivery. The best [Ru(bipy)3 ]2+ delivery inhibitors were ATP and hexametaphosphate anions. Inhibition was ascribed to the interaction of the anions with the grafted CuII complexes on the surface of the SC1, SC2, and SC3 supports. The hexametaphosphate anion was selected to prepare two capped materials (SC1-mPh and SC3-mPh). Studies of the [Ru(bipy)3 ]2+ dye release from solids SC1-mPh and SC3-mPh alone and in the presence of a collection of selected anions (HS- , F- , Br- , Cl- , I- , CN- , HPO42- , AcO- , citrate, NO32- , HCO3- , SO42- , and S2 O82- ), amino acids (alanine and histidine), thiol-containing biomolecules (cysteine, methylcysteine, homocysteine, and glutathione (GSH)), and oxidants (H2 O2 ) were performed. None of the chemicals tested, except hydrogen sulphide, was able to induce remarkable cargo delivery in both solids. The observed dye release was ascribed to a demetalation reaction of the C1 and C3 complexes induced by the hydrogen sulphide anion.

Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles.

Silica nanoparticles functionalized with thiol reactive units and bulky polar polyamines were used for the selective colorimetric detection of formaldehyde. The reaction of thiols groups in the nanoparticles surface with a squaraine dye resulted in loss of the π-conjugation of the chromophores, and the subsequent bleaching of the solution. However, when formaldehyde was present in the suspension, the thiol-squaraine reaction was inhibited and a chromogenic response was observed. A selective response to formaldehyde was observed only when the thiol and polyamine groups were anchored to the silica surface. The observed selective response was ascribed to the fact that bulky polyamines generate a highly polar environment around thiols, which were only able to react with the small and polar formaldehyde, but not with other aldehydes. The sensing nanoparticles showed a limit of detection (LOD) for formaldehyde of 36 ppb in water.

Anion Binding by Dimetallic Nickel(II) and Nickel(III) Complexes of a Face-to-Face Bicyclam: Looking for a Bimacrocyclic Effect.

The dinickel(II) complex of the face-to-face bicyclam ligand α,α'-bis(5,7-dimethyl-1,4,8,11-tetraazacyclotetradecan-6-yl)-o-xylene (L∩L) in a dimethyl sulfoxide solution exists as a mixture of high- and low-spin forms and uptakes up to three halide and pseudohalide ions (X(-)), according to stepwise equilibria, whose constants were determined through spectrophotometric titration experiments. In the case of halides, the first anion goes into the intermetallic cavity, whereas pseudohalides first coordinate the metal center from outside. Comparison with equilibrium data for the complex with the macrocycle 5,7-dimethyl-6-benzyl-1,4,8,11-tetraazacyclotetradecane (L) shows that the dinuclear complex [Ni(II)2(L∩L)](4+) displays an affinity for the first halide distinctly higher than the mononuclear complex [Ni(II)(L)](2+), thus disclosing the existence of a bimacrocyclic effect for anion binding. Differential pulse voltammetry studies typically showed a three-peak profile: the most anodic pertaining to the [Ni(II)2(L∩L)](4+) → Ni(III)2(L∩L)](6+) two-electron process, then one originating from the [Ni(II)2(L∩L)X](3+) → Ni(III)2(L∩L)X](5+) two-electron process, and one deriving from the two two-electron half reactions [Ni(II)2(L∩L)X2](2+) → Ni(III)2(L∩L)X2](4+) and [Ni(II)2(L∩L)X3](+) → Ni(III)2(L∩L)X3](3+), taking place at nearly the same potential. The crystal structure of the [Ni(II)2(L∩L)(µ-NCO)(NCO)2]ClO4·2.5H2O complex salt showed a caterpillar arrangement of the three metal-bound cyanate ions.

The interaction of Mozobil™ with carboxylates.

Mozobil(™) (1,1'-[1,4-phenylenebis(methylene)]bis[1,4,8,11-tetraazacyclotetradecane], 1, also known as JM3100 and AMD 3100) is a specific antagonist of the chemokine coreceptor CXCR4 and favours the mobilisation from the bone marrow of stem cells, which can be used for autologous transplantation. It is believed that the interaction, of both hydrogen bonding and electrostatic nature, involves a partly protonated form of Mozobil(™), LHn(n+) and the COO(-) groups of Asp(171) and Asp(262) residues protruding from the walls of the pocket of the membrane protein CXCR4. We have investigated, through potentiometric titrations in 0.1 M NaNO3 at 25 °C, the interaction equilibria between 1 (L) and linear dicarboxylates A(2-). These studies have demonstrated that the main equilibrium takes place: LH5(5+) + A(2-)⇄ [LH5···A](3+), and that the most stable [LH5···A](3+) complex forms for A(2-) = diphenyl-4,4'-dicarboxylate, whose length matches that of LH5(5+). (1)H NMR titration experiments have shown that in the 7-10 pH interval, LH3(3+), LH2(2+) and LH(+) forms establish π-π interactions with diphenyl-4,4'-dicarboxylate, according to a topological arrangement which excludes the formation of H-bonds. It is finally suggested that, in the pocket of the CXCR4 membrane protein, Mozobil(™) operates as a pentammonium cation, which establishes with carboxylate groups of Asp(171) and Asp(262) strong interactions of hydrogen bonding and electrostatic nature.

Copper(II) Complexes of Cyclams Containing Nitrophenyl Substituents: Push-Pull Behavior and Scorpionate Coordination of the Nitro Group.

The three nitrophenyl-cyclam derivatives (nitrocyclams): 1-(4-nitrophenyl)-1,4,8,11-tetraazacyclotetradecane (2), 1-(2-nitrophenyl)-1,4,8,11-tetraazacyclotetradecane (3), and 1-(2,4-dinitrophenyl)-1,4,8,11-tetraazacyclotetradecane (4), in an MeCN solution, specifically incorporate the Cu(II) ion according to an irreversible process signaled by disappearance of the yellow color for a concentration c < 1 × 10(-4) M and by a yellow-to-red color change for c ≥ 1 × 10(-3), and must be considered efficient and specific dosimeters of copper(II) salts. When present in the ortho position of the nitrophenyl substituent, the -NO2 group coordinates the Cu(II) according to a scorpionate mode, while the metallocyclam system exhibits a trans-I configuration. In an MeCN solution the red trans-I-[Cu(II)(3)](2+) and trans-I-[Cu(II)(4)](2+) scorpionate complexes slowly convert into the violet trans-III scorpionate complexes. Kinetic aspects of the trans-I-to-trans-III configurational rearrangement were investigated in detail for the [Cu(II)(4)](2+) system. In particular, the conversion is spectacularly accelerated by catalytic amounts of Cl(-), NCO(-), and F(-). While for Cl(-) and NCO(-) the effect can be associated with the capability of the anion to stabilize through coordination a possible dissociative intermediate, the amazingly powerful effect of F(-) must be related to the preliminary deprotonation of one N-H fragment of the macrocycle, driven by the formation of the HF2(-) ion. Most of the metal complex species studied in solution were isolated in a crystalline form, and their molecular structures were elucidated through X-ray diffraction studies. This study documents the first examples of effective metal coordination by the nitro group.