Post on 16-Mar-2022
1
Physicochemical properties of LanthanidesPhysicochemical properties of Lanthanides
Electronic levels: Term Symbols (ground state)Electronic absorption spectraLuminescence spectraMagnetism
0123
E / 103 cm-1
10.0
0
2F5/2
2F7/2
2’1’0’
Lecture 22
Swavey, S. J. Chem. Educ., 2010, 87 (7), 727–729
1
2
2
3
4
3
2.1 Electronic levels
(Summary from the BSc course “Coordination chemistry”2.1.1 Electronic structure of 4f elements
Russel-Saunders coupling usually works well
(2S+1)(2S+1)
S P D F G H I J K …0 1 2 3 4 5 6 7 8 = L
J = L+S, L+S-1…, |L-S|
spin multiplicity
(2S+1)J(2S+1)J
Spectroscopic termMultiplicity = (2S+1)´(2L+1)
Spectroscopic level, multiplicity = (2J+1)
Electronic States/Term symbols
Hund’s rules for ground state:
• Spin multiplicity must be the highest possible (Smax)
• If more than one term have the highest multiplicity,the term with the highest value of L is the groundstate (Lmax)
• The ground level has Jmin if the subshell is less thanhalf filled, Jmax if the subshell is more than halffilled
Example: Nd3+, 4f3
3 2 1 0 -1 -2-3 m ( = 3)
Lmax = 6 J = 15/2……9/2
4I9/24I9/2
Smax = 3´½ = 3/2
Electronic States/Term symbols-Ground state term symbols
5
6
4
Ground state Term Symbol for Sm3+
Work Out/Solution
7
8
5
Tb: [Xe]4f96s2
Tb3+: [Xe]4f8
Swavey, S. J. Chem. Educ., 2010, 87 (7), 727–729
Diagram representing the interactions leading to the splitting of the electronic energy levels of a Eu3+ ion
Notice minimal effect of ligand field
9
10
6
Interpret the Transiitons from the spectra
Ln3+ 4fn, n Groundlevel
Color Magnetic momentexp. calc.
Ce 1 2F5/2 colorless 2.3-2.5 2.54Pr 2 3H4 green 3.4-3.6 3.58Nd 3 4I9/2 lilac 3.5-3.6 3.62Pm 4 5I4 pink n.a. 2.68Sm 5 6H5/2 yellow 1.4-1.7 0.85Eu 6 7F0 pale pink 3.3-3.5 0Gd 7 8S7/2 colorless 7.9-8.0 7.94Tb 8 7F6 colorless 9.5-9.8 9.72Dy 9 6H15/2 yellow 10.4-10.6 10.6Ho 10 5I8 yellow 10.4-10.7 10.6Er 11 4I15/2 rose 9.4-9.6 9.58Tm 12 3H6 pale green 7.1-7.5 7.56Yb 13 2F7/2 colorless 4.3-4.9 4.54
Linking spectral and Magnetic properties
Figure out spectral and magnetic properties from term symbol
11
12
7
Electronic Absorption Spectra
Observe: Very low molar absorption coefficient (y-axis)Frame a question!!! On why this value is very small.
Pr(Tf2N)3 10-2 M in BumimTf2N
0
0.002
0.004
0.006
0.008
0.01
0.012
400 450 500 550 600 650
abso
rban
ce
N NN
SO O
F3CS
O O
CF3 PrIII 4f2, 3H4
0
5
10
15
20
25E / 103 cm-1
1G4
1D2
3H
3F
1I6
3P
456234
012
3PJ
1D2
01
2
1I6
/nm
Tf2N
Absorption spectral properties
13
14
8
Jablonski diagram
15
16
9
Luminescence spectra
Basics of luminescence
S1
S2
S0
T1
F PA
S = singlet
T = triplet
E0
E2
E1
energy A = absorption10-16 s
F = fluorescence10-12-10-6 s
P = phosphorescence10-6 – 10s
non-radiativede-activationintersystemcrossing
Jablonski’s diagram (organic molecules)
17
18
10
singlet S1 triplet T1
intersystem
crossingone electronchanges its spin
Fluorescence : without spin changePhosphorescence : with spin changeFluorescence : without spin changePhosphorescence : with spin change
Indirect excitation, called sensitisation is achieved throughlattice or attached ligands
light harvesting
hn hn
hnhn
Energy transfer light emision
The excited states of LnIII ions are usually long-lived withlifetimes in the range ms to ms, so that the ligand tripletstate plays a major role in the energy transfer process.
Physico-chemical properties of Lanthanides-Indirect Sensitization
19
20
11
Absorption
LnIII
4f*
Ligand
1S*
Ground state
3T*
Complex
Energy transfer
Non radiative deactivation
Quenching or back transfer
F
P
E
20 rate constants ! Complicated energy transfer
pathways
Energy migration paths
Physico-chemical properties
Many competitive pathways…
21
22
12
4f emission spectra
Pr Nd Sm Eu
Tb Dy Ho Er Tm Yb
0
5
10
15
20
25
30
35
40
0
5
10
15
20
25
30
35
40
E/ 1
03
cm-1
3H4 4I9/2
6H5/27F0,1
8S7/2 7F6
6H15/2 5I8 4I15/2
3H6 2F7/2
1D2
3P0
4F3/2
4G5/25D
01
2
6P7/2
5D4
5D3
4F9/2
5S24S3/2
1D2
1G4
2F5/2
Gd
1G4
4I13/2
3P0
3F4
5F5
Chapter 2 Physico-chemical properties
23
24
13
Energy level diagrams for lanthanides
Bünzli, J. C. G. et al. Chem. Soc. Rev. 2005, 34, 1048-1077
The main luminescent levels are drawn in red, while the fundamental levels is indicated in blue
Electronic levels: 14!/n!(14 -n)!Eu(III) and Tb(III): 3003 Gd(III): 3432
25
26
14
27
28
15
29
30
16
31