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Experiment 4 Spectroscopic study of Cu(II) Complexes: Crystal Field ...

Experiment 4 Spectroscopic study of Cu(II) Complexes: Crystal Field ...

Experiment 4 Spectroscopic study of Cu(II) Complexes: Crystal Field

Experiment 4 Spectroscopic study of Cu(II) Complexes: Crystal Field Theory Objective: To study the effect of ligands on crystal field splitting energy (E) Theory The color of coordination compounds of the transition elements is one of their characteristic properties. These colors are due to the absorption and subsequent emission of light in the visible part of the spectrum. Light in this region of the spectrum caused promotion of d–electrons from a lower to a higher energy level. The spectra which result are generally referred to as Electronic Spectra. Note that electronic transitions may also be effected by ultraviolet light. Because of the size of the quanta involved, electronic transitions in molecules are always accompanied by vibrational and rotational changes, and hence a band spectrum is observed. In general, the bands which arise are much broader than bands in an infrared spectrum and are little used for identification purposes. The crystal field theory of bonding in transition metal complexes has help appreciably to rationalize many of the physical properties of such complexes. Much of the data required for crystal field theory calculation is obtained from a study of the absorption spectra of transition metal complexes. Regularly six–coordination is most readily pictured by placing the ligands at the plus and minus ends of the three coordinate axes. An electron in the d X 2 - y 2 and d z 2 orbitals is therefore most effected by the field of the ligands and is raised in energy relative to an electron in the d xy , d yz and d zx orbitals. The combined energy level diagram is therefore composed of two upper orbitals, of equal energy, and three lower orbitals, which are also degenerate (Figure 4.1). The energy zero is conveniently taken as the weighted mean of the energies of these two sets of orbitals; the lower trio are thus stabilized by -2/5 E while the upper pair are destabilized by 3/5E, where E is the total energy separation. It is termed the crystal field splitting energy. The e g and t 2g symbols are symmetry labels arising from Group theory and are now the most commonly used symbols.

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