[1-B<Subscript>10</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>]<Superscript>−</Superscript> and [1-CB<Subscript>9</Subscript>H<Subscript>10</Subscript>]<Superscript>−</Superscript> anions: an attempt of quantum chemical calculations

Comparative quantum chemical calculations of structural parameters, chemical shifts of ¹¹B NMR spectra, and atomic charges in 10-vertex boron hydride anions [1-CB₉H₁₀]⁻ and [1-B₁₀H₉N₂]⁻ were performed using the restricted Hartree-Fock method with the 6-31++G(D,P) basis set. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1853–1855, September, 2007.     

Raman spectroscopic study of the hydration of short-chain poly(oxyethylene)s C <Subscript>1</Subscript>E<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C <Subscript>1</Subscript> (<Emphasis Type="Italic">n</Emphasis>=1−4)

The hypothesis that the degree of hydration of poly(oxyethylene) (POE) in aqueous solution depends on the mole ratio of water molecules to ether oxygen atoms in the molecule has been verified by studying the isotropic Raman spectra in the O−H stretching region for four short-chain POEs (C ₁E _n C ₁ withn=1−4). Excellent coincidence of the O−H stretching Raman band for all four POEs studied in the range of mole ratio H₂O/O _ether from 25 to 0.6 was observed, thus confirming the assumption stated above. A conclusion that all ether oxygen atoms in the POE molecule participate in hydrogen bonding with water molecules has been made.     

Interaction and Scale of Mixing in Cellulose Acetate/Poly(<Emphasis Type="Italic">N</Emphasis>-vinyl Pyrrolidone-co-vinyl Acetate) Blends

Binary blends and pseudo complexes of cellulose acetate (CA) with vinyl polymers containing N-vinyl pyrrolidone (VP) units, poly(N-vinyl pyrrolidone) (PVP) and poly(N-vinyl pyrrolidone-co-vinyl acetate) [P(VP-co-VAc)], were prepared, respectively, by casting from mixed polymer solutions in N,N-dimethylformamide as good solvent and by spontaneous co-precipitation from solutions in tetrahydrofuran as comparatively poor solvent. The scale of miscibility and intermolecular interaction were examined for the blends and complexes by solid-state ¹³C-NMR spectroscopy. It was revealed that the formation of complexes was due to a higher frequency of hydrogen-bonding interactions between the residual hydroxyl groups of CA and the carbonyl groups of VP residues in the vinyl polymer component. From measurements of CP/MAS spectra and proton spin-lattice relaxation times (T_1ρ^H) in the NMR study, the existence of the hydrogen-bonding interaction was also confirmed for the miscible blends and the homogeneity of the mixing was estimated to be substantially on a scale within a few nanometers.     

Determination of the primary structure and carboxyl p<Emphasis Type="Italic">K</Emphasis><Subscript>A</Subscript>s of heparin-derived oligosaccharides by band-selective homonuclear-decoupled two-dimensional <Superscript>1</Superscript>H NMR

Determination of the structure of heparin-derived oligosaccharides by ¹H NMR is challenging because resonances for all but the anomeric protons cover less than 2 ppm. By taking advantage of increased dispersion of resonances for the anomeric H¹ protons at low pD and the superior resolution of band-selective, homonuclear-decoupled (BASHD) two-dimensional ¹H NMR, the primary structure of the heparin-derived octasaccharide ∆UA(2S)-[(1 → 4)-GlcNS(6S)-(1 → 4)-IdoA(2S)-]₃-(1 → 4)-GlcNS(6S) has been determined, where ∆UA(2S) is 2-O-sulfated ∆^4,5-unsaturated uronic acid, GlcNS(6S) is 6-O-sulfated, N-sulfated β-d-glucosamine and IdoA(2S) is 2-O-sulfated α-l-iduronic acid. The spectrum was assigned, and the sites of N- and O-sulfation and the conformation of each uronic acid residue were established, with chemical shift data obtained from BASHD-TOCSY spectra, while the sequence of the monosaccharide residues in the octasaccharide was determined from inter-residue NOEs in BASHD-NOESY spectra. Acid dissociation constants were determined for each carboxylic acid group of the octasaccharide, as well as for related tetra- and hexasaccharides, from chemical shift–pD titration curves. Chemical shift–pD titration curves were obtained for each carboxylic acid group from sub-spectra taken from BASHD-TOCSY spectra that were measured as a function of pD. The pK _As of the carboxylic acid groups of the ∆UA(2S) residues are less than those of the IdoA(2S) residues, and the pK _As of the carboxylic acid groups of the IdoA(2S) residues for a given oligosaccharide are similar in magnitude. Relative acidities of the carboxylic acid groups of each oligosaccharide were calculated from chemical shift data by a pH-independent method.     

Functionalization of one or two methyl groups in the [Cp*<Subscript>2</Subscript>RuBr]<Superscript>+</Superscript>Br<Superscript>−</Superscript> complex in the reaction with bromine

The reaction of [Cp*₂RuBr]⁺Br⁻ with bromine in CH₂Cl₂ (CD₂Cl₂) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C₅Me₄CH₂Br]⁺Br₃ ⁻ (syn conformer), [Cp*Ru(Br)C₅Me₃(CH₂Br)₂]⁺ (syn and anti conformers), and [Ru(Br)(C₅Me₄CH₂Br)₂]⁺ (syn conformer). All complexes were characterized by ¹H and ¹³C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC₅Me₄CH₂]⁺BF₄ ⁻ with bromine in CH₂Cl₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005.     

Effects of ionization on the phase behavior of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-co-acrylic acid) and poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diethylacrylamide-co-acrylic acid) in water

Phase transitions of poly(N-isopropylacrylamide-co-acrylic acid) (PiPA-AA) and poly(N,N- diethylacrylamide-co-acrylic acid) (PdEA-AA) in water have been investigated by means of turbidimetry, Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The phase transition temperatures (T_p) of these copolymers increase with the degree of ionization () of the acrylic acid (AA) units, which in turn is dependent on the pH of the solutions. Apparent values of pK_a for the AA units, determined from the pH dependencies of T_p, are 4.7 and 5.4 for PiPA-AA and PdEA-AA, respectively. Differences between T_p for PiPA-AA and T_p for PiPA homopolymer (T_p) are +1.5 and –0.2 °C/mol% of AA at =1 and 0, respectively. The values of T_p for PdEA-AA are +2.6 (ionic) and –0.5 (nonionic)°C/mol%, indicating that the incorporated AA units have a larger effect on PdEA than on PiPA. DSC measurements performed with each of these copolymers at different pH values show a linear relationship between T_p and the enthalpy of transition (H). IR measurements of PiPA-AA show that the profiles of IR bands from both iPA and AA units exhibit critical changes at T_p of the copolymer. Heating the solution above T_p leads to shifts of the amide II, C–H stretch, and C–H bend bands from the iPA units toward lower wavenumbers, as well as a shift of the amide I band from the iPA units toward higher wavenumbers. A decrease in the intensity of the symmetric C=O stretch IR band from carboxylate anions (1560 cm^–1), and an increase in the intensity of the C=O stretch band from COOH groups (1705 cm^–1) suggest that a partial protonation of the carboxylate groups (COO^–+H⁺COOH) takes place upon the phase transition.     

Voltammetric determination of the trace amounts of bromate in drinking water after pre-concentration on hydrous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A differential pulse voltammetric (DPV) method for the determination of bromate in drinking water, after pre-concentration on γ-Al₂O₃, is proposed. The reduction peak of bromate has been observed at the potential E _p -−1.6 V in an ammonia buffer as a supporting electrolyte. The method has been successfully applied to determine a bromate concentration of 2.5 μg·l⁻¹ in drinking water (RSD=6.1%, n=7). A sample pre-treatment with a column filled with mixed cation-exchange resin in Ag, Ba and H forms was needed before pre-concentration of bromate on alumina.     

Ionic mobility in ammonium-rubidium heptafluorozirconate (NH<Subscript>4</Subscript>)<Subscript>2.4</Subscript>Rb<Subscript>0.6</Subscript>ZrF<Subscript>7</Subscript> by (<Superscript>1</Superscript>H, <Superscript>19</Superscript>F) NMR data

NMR (¹⁹F, ¹H) methods are used to study ionic mobility in heptafluorozirconate (NH₄)_2.4Rb_0.6ZrF₇ in a range of temperatures from 150 K to 430 K. Types of ionic movements are determined, and their activation energy is evaluated. As a result of a phase transition a modification forms in which diffusion in the ammonium sublattice and isotropic reorientations of ZrF ₇ ^3? complex anions are observed. According to preliminary data, due to diffusion of ammonium ions the compound has relatively high ionic conductivity (σ ≈ 8.3 × 10^?5 S/cm at 423 K).     

Synthesis and physicochemical study of Ni<Superscript>II</Superscript> complexes with tetradentate acyclic and macrocyclic N<Subscript>2</Subscript>S<Subscript>2</Subscript> ligands as thiosalen analogs

N,N’-Polymethylenebis(thiosalicylidene)iminate and macrocyclic dithiadiazadibenzocycloalkadiene complexes of nickel(II) were synthesized and their electrochemical and spectroscopic properties were studied. Dithiadiazadibenzocycloalkadiene complexes containing two DMSO molecules coordinated to Ni²⁺ and two outer-sphere ClO₄ ⁻ anions were synthesized by the reaction of the corresponding macrocyclic ligands with Ni(ClO₄)₂·6H₂O. The structure of 3,6-dithia-10,14-diazadibenzo[a,g]cyclopentadeca-9,14-dienylnickel(II)[bis(dimethyl sulfoxide) bis-perchlorate] was established by X-ray diffraction. The UV-Vis spectroscopic data are consistent with octahedral structures of diiminobis(sulfide) complexes, a square-planar structure of the thiosalen complex, and distorted tetrahedral structures of other diiminodithiolate complexes. The reaction of S-tert-butylthiosalicylaldehyde with hydrazine hydrate afforded di(ortho-tert-butylthiobenzal)azine. The reaction of the latter with anhydrous NiCl₂ produced a colored complex with the simplest molecular formula Ni(C₁₆H₁₂N₂S₂) in 15% yield. Semiempirical PM3(tm) calculations and the results of UV-Vis, ESR, and ¹H NMR spectroscopy demonstrate that this complex has most probably a dimeric structure, in which two Ni centers adopt a nearly square-planar configuration. The complexes are clearly divided into two types according to their electrochemical behavior in DMF solutions. The type 1 is characterized by reversibility of the first reduction steps. The type 2 is characterized by irreversible two-electron reduction as the first step accompanied by deposition of Ni metal on the electrode surface. Rapid electrochemically initiated alkylation occurs in the presence of various alkylating agents (BuⁿI, BuⁿBr, (DmgH)₂CoCH₃) in a solution of complex 1 in DMF.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–183, January, 2005.     

Co<Superscript>II</Superscript> and Rh<Superscript>I</Superscript> complexes with <Emphasis Type="Italic">C</Emphasis><Subscript>2</Subscript>-symmetric chiral diamines of the dioxolane series

The reaction of di-μ-chlorobis(1,5-cyclooctadiene)dirhodium with (4S, 5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane (1) gave the complex [Rh(cod)(1)]Cl (cod is 1,5-cyclooctadiene). The composition of the complexes CoCl₂ · L₂ and [Rh(cod)(L₂)]X (L₂ = 1, (4S,5S)-2,2-dimethyl-4,5-bis(aminomethyl)-1,3-dioxolane, and (4S, 5S)-2,2-dimethyl-4,5-bis(dimethylaminomethyl)-1,3-dioxolane; X = Cl, TfO) was studied using IR and ¹H NMR spectroscopy. In the Rh^I cyclooctadienediamine complexes, the diene molecule forms a stronger bond with the metal atom than that in the cyclooctadienediphosphine analogs. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2270–2274, October, 2005.     

Second Dissociation Constant of H<Subscript>2</Subscript>Te and the Absorption Spectra of HTe<Superscript>–</Superscript>, Te<Superscript>2–</Superscript> and Te<Subscript>2</Subscript><Superscript>2–</Superscript> in Aqueous Solution

We have measured the second acid dissociation constant, K _2a , at several ionic strengths for hydrogen telluride (H₂Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe⁻ and Te²⁻. Since it is produced in our solutions, we have also determined the spectra of Te₂ ²⁻ both in the uv and in the visible regions. At 25 ^∘C, K _2a = (1.28 ± 0.02) × 10⁻¹² by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm^-3 was estimated to be (8.7 ± 0.2) × 10⁻¹². The solution thermodynamics of these species are also discussed and comparisons are made to related acids.     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.     

Removal of <Superscript>60</Superscript>Co<Superscript>2+</Superscript> and <Superscript>137</Superscript>Cs<Superscript>+</Superscript> ions from low radioactive solutions using <Emphasis Type="Italic">Azolla caroliniana</Emphasis> willd. water fern

This study concerns the removal of the ¹³⁷Cs⁺ and ⁶⁰Co²⁺ β+γ-radioactive ions in Azolla caroliniana Willd. water fern. The living fern and two different types of biosorbent prepared from Azolla caroliniana were tested to remove the above-mentioned radioactive ions from dilute solutions, in the absence and in the presence of the ionic competition. Effective ¹³⁷Cs⁺ and ⁶⁰Co²⁺ ions removal from low radioactive wastewaters was demonstrated. The time dependent K _d (t) values were calculated from the absorption data. These results indicate that removal process achieved equilibrium in about 120 min and that it involves two steps: rapid and slow absorption; the active process (metabolic bioaccumulation on the living fern) was responsible for above one half of the total removal process. A thin layer radiochromatography study leads to the conclusion that the biochemical components in which ¹³⁷Cs⁺ and ⁶⁰Co²⁺ place themselves are of a polysaccharide and lipoid fractions.     

Synthesis,crystal structure,and <Superscript>1</Superscript>H NMR spectra of a chloride-bridged chain complex of dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-<Emphasis Type="Italic">d</Emphasis><Subscript>5</Subscript>)benzoate

Deuterated dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-d ₅)benzoate, [Ru₂{3,4,5-(C₂D₅O)₃C₆H₂-COO}₄Cl] _n , was synthesized by a reaction of [Ru₂(C₂H₅COO)₄Cl] _n and 3,4,5-tri(ethoxy-d ₅)benzoic acid and characterized by single-crystal X-ray analysis as well as IR, UV-VIS, and ¹H NMR spectra, and compared with those of the undeuterated complex [Ru₂{3,4,5-(C₂H₅O)₃C₆H₂COO}₄Cl] _n . Single-crystal X-ray analysis showed that chloride ligands bridge the dinuclear ruthenium(II,III) units at the axial positions to form a zigzag chain molecule with the Ru¹-Cl-Ru² angle of 123.82(4)°. ¹H NMR spectra in CD₂Cl₂ displayed a broad signal attributable to o-H atoms on the phenyl rings of the benzoate ligands from approximately δ = 23 to δ = 32 at 25°C and several signals from approximately δ = −50 to δ = 50 at −80°C. These spectra show the preservation of the polymeric or oligomeric chain structure in dichloromethane, which is supported by the solution behavior confirmed by the UV-VIS spectra and electronic conductance.     

Photophysical and electrochemical properties of the outer-sphere associate of [Ru(bipy)<Subscript>3</Subscript>]<Superscript>2+</Superscript> with <Emphasis Type="Italic">p</Emphasis>-sulfonatothiacalix[4]arene

¹H NMR titration and X-ray diffraction analysis revealed that [Ru(bipy)₃]²⁺ forms an outer-sphere inclusion complex with p-sulfonatothiacalix[4]arene in a ratio of 1: 1 in both aqueous solutions and the solid state. According to cyclic voltammograms and fluorimetric data, the outer-sphere association of [Ru(bipy)₃]²⁺ with p-sulfonatothiacalix[4]arene changes the reversible character of the electrochemical oxidation of [Ru(bipy)₃]²⁺ and lowers its emission intensity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1863–1870, September, 2008.     

Local structure and photoluminescent characteristics of Eu<Superscript>3+</Superscript> in ZnO–SiO<Subscript>2</Subscript> glasses

The photoluminescence properties of xZnO–(100−x)SiO₂ (x = 0, 5, 10, 20) containing 1% Eu₂O₃ prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of ⁵D₀–⁷F_J transitions of Eu³⁺ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu³⁺ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu³⁺ ions occupied one site in SiO₂ glass and two sites in ZnO–SiO₂ glasses. The second-order crystal field parameters were calculated. B₂₀ and B₂₂ for site 1 increased with excitation energy, while ones hardly changed for site 2.     

Reaction of Sulfur and Oxygen-Bridged 8-Quinolinolato Trinuclear Molybdenum Cluster [Mo<Subscript>3</Subscript>OS<Subscript>3</Subscript>(qn)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> with Acetylene Carboxylic Acids

The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo₃OS₃(qn)₃(H₂O)₃]⁺ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid, and pimelic acid gave clusters having μ-carboxylato groups, [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡CCOO)] (6), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₂COO)] (7), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₃COO)] (8), [Mo₃OS₃(qn)₃(H₂O)(μ-CH₃COO)] (4), and [{Mo₃OS₃(qn)₃(C₂H₅OH)}₂(μ-C₇H₁₀O₄)] (5), respectively. X-ray structural analyses, ¹H NMR, and electronic spectra of these clusters made clear that each of the COO⁻ groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters. The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo₃OS(μ₃-SCH=C(COOH)S)(qn)₃(H₂O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as supported by the electronic and ¹H NMR spectra. The corresponding aqua cluster [Mo₃OS₃(H₂O)₉]⁴⁺ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo₃OS(μ₃-SCH=C(COOH)S)(H₂O)₉]⁴⁺ (2). Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Study on Inclusion Complex Formation of <Emphasis Type="Italic">m</Emphasis>-Aminobenzoic Acid with Native and Substituted <Emphasis Type="Italic">β</Emphasis>-Cyclodextrins

The complex formation of native and substituted β-cyclodextrins with m-aminobenzoic acid in water was characterized by calorimetry, ¹H NMR and UV spectroscopic studies. These studies showed that β-, hydroxypropyl-β- and methyl-β-cyclodextrins form 1:1 inclusion complexes with m-aminobenzoic acid. The thermodynamic properties of complex formation (K,Δ_c G ^o,Δ_c H ^o,Δ_c S ^o) were calculated. It was found that the processes of complexation are mainly favorable entropically. Introduction of hydroxypropyl- and methyl-substituents into the β-CD molecule results in negligible enhancement of stability of the complexes formed. The structure of these substituents has no influence on the stability constant values. The insertion of the carboxylic group of m-aminobenzoic acid into the cyclodextrin cavity was confirmed by ¹H NMR data.     

Association behavior of one-end hydrophobically modified poly[<Emphasis Type="Italic">N</Emphasis><Superscript>5</Superscript>-(2-hydroxyethyl) <Emphasis Type="SmallCaps">l</Emphasis>-glutamine] in water/ethylene glycol mixed solvent

Amphiphilic polymers Cn-PHEG consisting of water-soluble poly[N ⁵-2-(hydroxyethyl) l-glutamine] (PHEG) and hydrophobic alkyl chain (carbon number n = 12, 14, 16, or 18) attached at the PHEG terminal was prepared, and association behavior and structure of associate for Cn-PHEG in selective solvent (water/ethylene glycol mixed solvent) have been investigated. α-Helix content of PHEG block for all the polymers increased with weight fraction of ethylene glycol in the mixed solvent (W _EG). By light scattering measurements, formation of a small micelle was suggested for C14-, C16-, and C18-PHEG when W _EG = 0. With the increase in W _EG, appearance of a larger associate was revealed for C16- and C18-PHEG. Evaluated molecular weight and radius of gyration suggested that the micelle is star-like sphere when W _EG = 0 and worm-like cylinder when W _EG = 0.7. C12-PHEG did not demonstrate any distinct micellization behavior because of the weak hydrophobicity of C12 chain.     

Gas phase structure of micro-hydrated [Mn(ClO<Subscript>4</Subscript>)]<Superscript>+</Superscript> and [Mn<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>+</Superscript> ions probed by infrared spectroscopy

Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO₄)(H₂O) _n ]⁺ and [Mn₂(ClO₄)₃(H₂O) _n ]⁺ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 2600–3800 cm⁻¹ spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO₂ laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of water—perchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 800–1700 cm⁻¹, we were also able to characterize the coordination mode (η²) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate Cl—O stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.