Series Preface.Preface.Acronyms, Abbreviations and Symbols.About the Author.1. Introduction.1.1 Electromagnetic Radiation.1.2 Infrared Absorptions.1.3 Normal Modes of Vibration.1.4 Complicating Factors.1.4.1 Overtone and Combination Bands.1.4.2 Fermi Resonance.1.4.3 Coupling.1.4.4 Vibration-Rotation Bands.References.2. Experimental Methods.2.1 Introduction.2.2 Dispersive Infrared Spectrometers.2.3 Fourier-Transform Infrared Spectrometers.2.3.1 Michelson Interferometers.2.3.2 Sources and Detectors.2.3.3 Fourier-Transformation.2.3.4 Moving Mirrors.2.3.5 Signal-Averaging.2.3.6 Advantages.2.3.7 Computers.2.3.8 Spectra.2.4 Transmission Methods.2.4.1 Liquids and Solutions.2.4.2 Solids.2.4.3 Gases.2.4.4 Pathlength Calibration.2.5 Reflectance Methods.2.5.1 Attenuated Total Reflectance Spectroscopy.2.5.2 Specular Reflectance Spectroscopy.2.5.3 Diffuse Reflectance Spectroscopy.2.5.4 Photoacoustic Spectroscopy.2.6 Microsampling Methods.2.7 Chromatography-Infrared Spectroscopy.2.8 Thermal Analysis-Infrared Spectroscopy.2.9 Other Techniques.References.3. Spectral Analysis.3.1 Introduction.3.2 Group Frequencies.3.2.1 Mid-Infrared Region.3.2.2 Near-Infrared Region.3.2.3 Far-Infrared Region.3.3 Identification.3.4 Hydrogen Bonding.3.5 Spectrum Manipulation.3.5.1 Baseline Correction.3.5.2 Smoothing.3.5.3 Difference Spectra.3.5.4 Derivatives.3.5.5 Deconvolution.3.5.6 Curve-Fitting.3.6 Concentration.3.7 Simple Quantitative Analysis.3.7.1 Analysis of Liquid Samples.3.7.2 Analysis of Solid Samples.3.8 Multi-Component Analysis.3.9 Calibration Methods.References.4. Organic Molecules.4.1 Introduction.4.2 Aliphatic Hydrocarbons.4.3 Aromatic Compounds.4.4 Oxygen-Containing Compounds.4.4.1 Alcohols and Phenols.4.4.2 Ethers.4.4.3 Aldehydes and Ketones.4.4.4 Esters.4.4.5 Carboxylic Acids and Anhydrides.4.5 Nitrogen-Containing Compounds.4.5.1 Amines.4.5.2 Amides.4.6 Halogen-Containing Compounds.4.7 Heterocyclic Compounds.4.8 Boron Compounds.4.9 Silicon Compounds.4.10 Phosphorus Compounds.4.11 Sulfur Compounds.4.12 Near-Infrared Spectra.4.13 Identification.References.5. Inorganic Molecules.5.1 Introduction.5.2 General Considerations.5.3 Normal Modes of Vibration.5.4 Coordination Compounds.5.5 Isomerism.5.6 Metal Carbonyls.5.7 Organometallic Compounds.5.8 Minerals.References.6. Polymers.6.1 Introduction.6.2 Identification.6.3 Polymerization.6.4 Structure.6.5 Surfaces.6.6 Degradation.References.7. Biological Applications.7.1 Introduction.7.2 Lipids.7.3 Proteins and Peptides.7.4 Nucleic Acids.7.5 Disease Diagnosis.7.6 Microbial Cells.7.7 Plants.7.8 Clinical Chemistry.References.8. Industrial and Environmental Applications.8.1 Introduction.8.2 Pharmaceutical Applications.8.3 Food Science.8.4 Agricultural Applications.8.5 Pulp and Paper Industries.8.6 Paint Industry.8.7 Environmental Applications.References.Responses to Self-Assessment Questions.Bibliography.Glossary of Terms.SI Units and Physical Constants.Periodic Table.Index.

Infrared Spectroscopy: Fundamentals and Applications

The properties of organic liquids that are relevant to their use as solvating solvents

Fluoride is often added to drinking water and toothpaste because of its beneficial effects in dental health. It is also administered in the treatment of osteoporosis.1 While the beneficial effects of fluoride are well documented, chronic exposure to high levels of this anion can lead to dental or even skeletal fluorosis.2-4 Taking into account these adverse effects, a great deal of attention has been devoted to the discovery of improved analytical methods for the detection of fluoride, especially in water. This field of research has also been stimulated by the potential use of such methods for the detection of phosphorofluoridate nerve agents such as Sarin or uranium hexafluoride, which release fluoride upon hydrolysis. In addition to these applications, the capture of fluoride, especially in water, is a stimulating academic challenge because of the high hydration enthalpy of this anion (∆H° ) -504 kJ mol-1). * To whom correspondence should be addressed. E-mail: simon.aldridge@ chem.ox.ac.uk (S.A.) and francois@tamu.edu (F.P.G.). † Texas A&M University. ‡ University of Oxford. Casey Wade was born in 1983 in Lynch, Nebraska. He earned a B.S. degree from the University of NebraskasLincoln in 2006. During his time there, he worked as an undergraduate researcher under the supervision of J. A. Belot and participated in a joint research internship at the American Air Liquide Chicago Research Center. In 2007, he joined the group of F. P. Gabbaı̈ at Texas A&M University, where he currently studies anion recognition using main group Lewis acids.

Fluoride Ion Complexation and Sensing Using Organoboron Compounds

The electrophilic properties of 34 solvents have been characterized by the Acceptor Number (AN) which has been derived from31P-n.m.r. measurements of triethylphosphine oxide dissolved in the respective solvents. Relationships are found between the acceptor numbers and theZ-values,E
T-values andY-values, as well as the free energies of solvation of anions and the redox potentials of the hexacyanoferrate(III)—hexacyanoferrrate(II) system in different solvents. The new parameter provides—together with the donor number—a useful guide in choosing the most appropriate solvent for a given reaction.

The acceptor number — A quantitative empirical parameter for the electrophilic properties of solvents

Solvent effects on the reactivities of organometallic compounds

Coordination reactions in non aqueous solutions - The role of the donor strength

Transition metal complexes of the composition [Fe(4-X-bzimpy)2](ClO4)2 [bzimpy = 2,6-bis-(benzimidazol-2′-yl)pyridine and X=H, OH, Cl] show thermally accessible spin-crossover behaviour in solution that depends on both the ligand and the solvent.1H-NMR spectroscopy and UV-visible spectroscopy measurements suggest that ligand substituent effects, solvent donor-acceptor properties and hydrogen-bonding may be employed to “fine-tune” the ligand field strength and hence to affect the spin-crossover behaviour. The ligand substitution changes in solution are reflected by the magnetic data (X=H:μexp=2.50 μB; X=OH:μexp=4.20 μB and X=Cl:μexp=4.30 μB at 294 K in MeOH), and by the shift of metal-to-ligandcharge-transfer band (X=H, λ=557 nm; X=OH, λ=520 nm; X=Cl, λ=500 nm). [Fe(bzimpy)2](ClO4)2 exhibits a pronounced spin-crossover equilibrium (1A1 →5T2) in solution (Ksc=0.26 at 293 K; μexp=1.30 → 3.40 μB for 213 → 328 K in MeOH). A small variation of magnetic moments of [Fe(4-OH-bzimpy)2](ClO4)2 (μexp=3.77 → 4.73 μB at 220 → 332 K) might indicate either the existence of (temperature dependent) hydrogen bonding between the ligand and solvent molecules or a temperature dependent variation in the population of the5Eg sublevel. The presence of strong donor solvents (DN ⩾ 30) shifts the spin-state of the complexes.

Spin-Crossover Complexes in Solution. III. Substituent- and Solvent Effects on the Spin-Equilibrium of 4-substituted Iron(II)-2,6- bis-(benzimidazol-2'-yl)-pyridine systems

Structural and electronic responses of coordination compounds to changes in the molecule and molecular environment

The solvatochromic and thermochromic behaviour of a series of mixed Ni(II) complexes with unsubstituted and substituted β-diketones and diamines in the solvents 1,2-dichloroethane (DCE), acetonitrile (An), acetone (AC),n-butanol (n-BuOH), formamide (FA), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (PY) has been studied and characterized on the basis of electronic spectra. Spectrophotometric methods have been used to evaluate equilibrium constants and their enthalpic and entropic terms for the formation of Ni(β-dik)(diam)L
+ and Ni(β-dik)(diam)L

 2
 +
 . Increasing donor strength of the donor-solvents (L) and (or) increasing electronwithdrawing parameters of the substituents at the β-diketone and the diamine ligands lead to increasing formation constants, paralleled by relative increase in the stability of the five-coordinated species Ni(β-dik)(diam)L
+. The results are discussed in terms of the extended donor-acceptor concept.

Viktor Gutmann

Papers

The acceptor number — A quantitative empirical parameter for the electrophilic properties of solvents

Coordination reactions in non aqueous solutions - The role of the donor strength

Spin-Crossover Complexes in Solution. III. Substituent- and Solvent Effects on the Spin-Equilibrium of 4-substituted Iron(II)-2,6- bis-(benzimidazol-2'-yl)-pyridine systems

Structural and electronic responses of coordination compounds to changes in the molecule and molecular environment

Spectroscopic and thermodynamic studies on solvatochromic nickel(II) complexes