This module develops the use, application and interpretation of molecular spectroscopies together with analytical approaches to purification. The application of these techniques to deduce the molecular structures of a wide variety of organic and inorganic compounds will be described. Primary focus will be on the application of Infrared, UV-visible absorption and nuclear magnetic resonance (NMR). Modern chromatographic purification techniques (HPLC, GCMS) will also be described in the context of identifying molecular species.

Knowledge and Understanding

1. Describe the underlying physical principles behind modern spectroscopic techniques;
2. Describe qualitatively and quantitatively the information provided by 1D and 2D NMR, IR, and UV-vis spectroscopies and mass spectrometry;
3. Relate the appearance of IR, UV-vis, 1D and 2D NMR and mass spectra to the relevant structures and physical properties of the molecular species;
4. From an appreciation of molecular form and structure predict the appearance of IR, UV-vis and NMR spectra for a wide variety of organic and inorganic molecules;
5. Understand the fundamental basis of chromatography and the physical origins of separation;
6. Discuss column design, support phase performance and ‘theoretical plates’;
7. Describe the common methods of post-chromatographic product detection based on UV-vis and MS analyses;
8. Prepare samples, operate spectrometers, and obtain qualitative and quantitative information from IR and UV-vis spectra.

 Intellectual Skills

1. Deduce appropriate chromatographic purification procedures and spectroscopic methods for identifying molecular compounds;
2. Analyse and interpret spectroscopic data to deduce detailed information about the molecular structure and physical properties of inorganic and organic compounds;
3. Utilise appropriate combinations of spectroscopic data to identify molecular structures.

The module will consist of 33 x 1 hour lectures; 24 (8 x 3) hours problem-based workshops: 4 x 3 hr NMR, 1 x 3 hr IR (group theory), 1 x 3 hr UV-vis (Tanabe-Sugano), 1 x 3 hr MS (etc.), 1 x 3 hr combination of all; 20 (4 x 3 + 2 x 4) hours of practical; 4 x 1 hour tutorial.

Chemistry-specific skills are based upon developing an understanding and appreciation of the spectroscopic properties of organic and inorganic compounds and the use of spectroscopic techniques to deduce molecular structure and compound purity.  More generally, strong skill elements of the module are transferable: data analysis and problem solving underpin the majority of the module content and the student-led activities.

A written exam (3 h) will test the student’s knowledge and understanding as elaborated under the learning outcomes. The coursework (workshops and tutorials) will allow the student to demonstrate his/her ability to judge and critically review relevant information.  Practical skills will be assessed via a series of laboratory-based exercises.

Autumn

Applied NMR Spectroscopy (7L)

Revision of key concepts (coupling, resonant frequencies);

1D NMR spectra , I = ½ (including ¹H, ¹³C, ¹⁹F, ³¹P, ¹⁰³Rh, ²⁹Si);

Decoupled spectra;

DEPT;

Satellites (i.e. non-100% abundant nuclei);

Chemical vs magnetic inequivalence in inorganic and organic systems;

Magnitude of coupling constants;

Fluxionality (Berry mechanism, coalescence temperature);

Prediction and analysis of NMR spectra for given molecular compounds;

Applied UV-vis Spectroscopy (5L)

Appearance of bands; vibronic structure;

Types of transition (π-π*, d-d, f-f, ILCT, MLCT, LMCT) and selection rules;

Relationship of electronic transitions to molecular structures;

Types of chromophore (including push-pull CT species);

Solvent dependence (positive and negative solvatochromism) of transitions and the nature of electronic transitions;

Chromatographic Techniques (5L)

Separation procedures;

Application to HPLC, GC, LC etc;

Ion exchange chromatography;

Detectors (incorporating Mass Spectrometry i.e. GCMS)

Spring

Applied IR Spectroscopy (4L)

Sample handling; effects of phase;

Structural information; vibrational modes;

Fingerprints; group frequencies;

Isotopic substitution (H/D);

Modes of ligand binding (linkage isomerism);

Application of group theory to M-CO complexes; prediction of bands from symmetry.

Applied NMR Spectroscopy part 2 (7L)

Monitoring reactions;

Exchange reactions and peak shape;

Applications of 2D NMR (COSY, HETCOR);

NMR spectra of quadrupolar nuclei (including ⁷Li, ^10/11B, ¹⁴N, ²⁷Al, ⁵⁵Mn, ⁷³Ge);

Application of quadrupolar NMR spectroscopy to main group and transition metal systems;

Applied UV-vis Spectroscopy part 2 (5L)

Revision of term symbols;

Electronic transitions and ligand field theory; spectrochemical series and ligand type;

Spectra of O_h vs. T_d;

Jahn-Teller effects;

Symmetry and Tanabe-Sagano diagrams;

Orgel diagrams;

Racah B/C parameters and ligand donor type;

Use of UV-vis spectroscopy in deducing ligand substitution reactions at TM, oxidation states of metal ions and symmetry.

Oxford Chemistry Primers: NMR spectroscopy in Inorganic Chemistry, J. A. Iggo, OUP.

Oxford Chemistry Primers: NMR, P. J. Hore, OUP.

Structural Methods in Inorganic Chemistry, Ebsworth, Rankin, Cradock, Blackwell Science.

Oxford Chemistry Primers: Inorganic Spectroscopic Methods, A. K. Brisdon, OUP.

Fundamental of Molecular Spectroscopy, C. N. Banwell, McGraw-Hill.

Modern Spectroscopy, J. M. Hollas, Wiley.

The Chemical Bond, Murrell, Kettle, Tedder.