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Electronic/UV-Vis/Absorption Spectroscopy
This is based on the movement of an electron from a ground state to an excited state, each
transition will relate to a discrete energy value characteristic to the system being analysed, allowing
structures to be calculated. The absorbance is dependent on the Beer-Lambert law;
A = εcl
The probability of the absorption occurring is given by the value of ε, the extinction coefficient.
For inorganic compounds this method is mainly used to analyse d-d transitions, these are generally
weak transitions performed in the visible region of light, and charge transfer processes in transition
metal complexes.
The spectra can give the crystal field splitting parameter (∆ or 10Dq), tell whether the species is high
or low spin and give the geometry (e.g. octahedral or tetrahedral, metal oxidation states, ligand
properties). Since d-d transitions are normally in the visible region, most transition metal complexes
are coloured (if they absorb through the visible they are black, if partially they display the
complimentary colour to that absorbed, if not at all they are white) and give broad absorption peaks,
this is since electronic transitions are rapid (around 10 -15s) and so molecules are in many vibrational
states at the time of the transition leading to absorption of a range of energies.
The most common geometry in transition metal chemistry is octahedral, where the 6 ligands lie on
the x,y and z axes, in this arrangement the greatest interaction occurs with the dx2 and dx2-y2 (the
t2g) orbitals as they lie along the axes, the remaining orbitals (the eg, dxy, dxz and dyz orbitals) lie
between the axes reducing the interaction.
In a tetrahedral geometry the ligands approach the dxy, the dxz and the dyz orbitals, the t2 orbitals,
while the dx2 and dx2-y2 remain at a lower energy, the e orbitals.
The probability of a transition occurring, effectively the value of ε, is given by three selection rules.
I-<Br-<Cl-<F-<O2-<H2O<NH3<CN-<PR3<CO
Tetrahedral Complexes
Since in a tetrahedral complex the crystal field splitting energy is 4/9 of that in an octahedral
complex d-d transitions occur at a lower energy (and so a higher wavelength) than those in an
octahedral complex. Also of importance is that tetrahedral complexes do not have a centre of
symmetry, so d-d transitions do not break the Laporte selection rule. If the spin selection rule is
obeyed then d-d absorptions are more intense than for octahedral complexes.
MLCT requires a low oxidation state metal and a reducible ligand e.g. [Ru(bipy)3]2+ which shows
MLCT absorption at 450nm.
The nuclear spin is quantised and given the quantum number I. I can be an integral or half-integral
and nuclei with spin larger than ½ are quadrupolar and typically give broad lines.
Nuclear spin, I, has 2I+1 mI states (with values +1 to -1) which in the absence of a magnetic field are
degenerate.
When placed in a magnetic field (strength equal to B0) their degeneracy is removed giving 2I+1
energy levels with mI states, with the lower levels only slightly more populated (~1 in 10 5 at 25oC)
according to the Boltzmann distribution, making the NMR signals weak.
The selection rule for NMR is that transitions must have a ∆m I=±1, the energy level of each state is
given by;
E = B0 γhmI
Where γ is the gyromagnetic ratio
Therefore to increase the strength of the NMR signal, the strength of the applied magnetic field may
be increased. Since ∆mI is limited to ±1 the energy differences are equal and proportional to γ, this is
different for all nuclei providing characteristic values of E. As different nuclei have different E values,
they will resonate at different frequencies.
Scalar Coupling
When there are different NMR active nuclei present in a molecule, scalar coupling will occur
between them. This arises as the nuclear magnetic moment of other NMR active nuclei surrounding
the nuclei of interest produce additional, albeit small, magnetic fields. If it occurs between the same
nuclei in different environments it is called homonuclear coupling, and if it is between different
elements it is called heteronuclear coupling. The observed nuclei are affected by these resultant
magnetic fields, the number and nature will depend on the nature of the surrounding active nuclei.
This effect is independent of the strength of the applied field and so the coupling constants will not
vary between NMR machines.
Scalar coupling is actually a polarisation of the electrons within the bonds between the nuclei, if one
nuclei is to spin upwards then an electron, in an orbital between this nuclei and the coupling nuclei,
can minimise its energy by aligning to spin in the same direction. As the electron on the coupled
nuclei is in the same orbital it must have the opposite spin, and how this interacts with the nuclear
spin of B will affect the energy of the spin state, perturbing the energy levels of the spin system.
In essence the nuclear spin of the first nuclei can sense that of the second due to polarisation of
electrons in bonds. The spin state of the second nuclei can affect the resonance energy and lead to
various multiplicities.
As the number of bonds between the nuclei increases the polarisation effect will decrease, as such it
is uncommon to observe coupling over more than 4 bonds.
In a situation where one of the nuclei has a spin of 3/2 there are 4 m I states (2I+1). The other nuclei
can sense the 4 different spin states which are all equally probably and so the first nuclei is split into
4 lines of equal intensity. In general, when a nuclei is coupled to a nuclei of spin I, the observed
multiplicity is;
2nI + 1
PF5 has a trigonal bypyramidal structure, single crystal x-ray studies indicate there are two distinct P-
F bonds (axial and equatorial) with P-Faxial=158.0pm and P-Fequatorial=152.2pm. For this species to be
spectroscopically detected it would have to exist in that energy state for a finite time. The
approximate timescale for NMR is 10-7 seconds (varying depending on the applied field and species
being studied as well as the species relaxation rate). The species PF5, at room temperature, is
fluxional, with fluorine atoms exchanging amongst each other. Since this occurs at a rate faster than
the NMR timescale only an average environment is observed, in which all fluorine atoms are
equivalent and not coupled to each other (just to the phosphorus). The process, by which the
fluorine atoms interchange, is known as Berry pseudo-rotation. To prevent this mechanism
interfering with the NMR spectra the species can be cooled down, the temperature at which this
mechanism is halted is known as the coalescent temperature.
Abundance of Isomer
Relative Intensity =
No .of Lines
The superimposed patterns would have the same central point but with different couplings.
Chemical Shift
The chemical shift of a peak or set of peaks is effected by the shielding of a nucleus, the less shielded
the nucleus is the more positive the shift value. An electronegative substituent, a positive charge or
a higher oxidation state will affect the ability of the electrons to shield the nucleus, leading to de-
shielding and a downfield shift in δ, the chemical shift.
Infrared/Vibrational Spectroscopy
Molecules undergo a complex series of vibrations which depend on;
-the symmetry of the molecule
-mass of the bonded atoms, as according to Hooke’s law;
1 k
Absorbed Frequency =
2πc μ
m1 m2
μ=
(m1 + m2 )
-bond strengths
Theory shows that these can be resolved into a limited number of normal modes of vibration. For a
molecule with ‘n’ atoms there will be 3n-6 vibrational modes if it is non-linear, and 3n-5 vibrational
modes if it is linear.
The selection rule for infrared spectroscopy is; a vibration will only absorb energy if a dipole change
occurs (the magnitude of the change is proportional to peak intensity).
As with organic compounds, inorganic bonds have characteristic absorption frequency ranges, the
position of a band can give the same sorts of information on bond strength, the mode of attachment
of ligands etc.
For MH;
1 k
νM−H =
2πc 1
For MD;
1 k
νM−D =
2πc 2
And so;
1
νM−H 1
= = 1.41
νM−D 1
2
∴ νM−D = 0.71(νM−H )
Linkage Isomers
Some ligands can coordinate to metal centres through different atoms, this gives rise to linkage
isomerism. Infrared spectroscopy can be used to help determine which type of coordination is
occurring. For example the nitro group, NO2-.
In the first example the absorption will be around 1300-1340cm-1 and 1350-1450cm-1, in the second
it will be around 1050-1200cm-1, indicative of an N-O single bond, and 1380-1480cm-1, indicative of
M=O character.