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Lect 18

The document discusses the lanthanide contraction effect where the radii of lanthanide ions decreases across the series due to the poor shielding of the 4f orbitals. This contraction leads to changes in properties like color, magnetism, and ability to form complexes. Lanthanide ions find applications as phosphors in lighting and security inks due to their characteristic colors from f-f transitions and ability to be sensitized by organic ligands or inorganic chromophores.

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46 views

Lect 18

The document discusses the lanthanide contraction effect where the radii of lanthanide ions decreases across the series due to the poor shielding of the 4f orbitals. This contraction leads to changes in properties like color, magnetism, and ability to form complexes. Lanthanide ions find applications as phosphors in lighting and security inks due to their characteristic colors from f-f transitions and ability to be sensitized by organic ligands or inorganic chromophores.

Uploaded by

JK JK
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Lanthanide Contraction

Atomic electron Ln3+ radius


Ln3+ electron
Element configuration (pm)
configuration
(all begin with [Xe]) (6-coordinate)
La 5d16s2 4f0 103
Ce 4f15d16s2 4f1 102
Pr 4f36s2 4f2 99
Nd 4f46s2 4f3 98.3
Pm 4f56s2 4f4 97
Sm 4f66s2 4f5 95.8
Eu 4f76s2 4f6 94.7
Gd 4f75d16s2 4f7 93.8
Tb 4f96s2 4f8 92.3
Dy 4f106s2 4f9 91.2
Ho 4f116s2 4f10 90.1
Er 4f126s2 4f11 89
Tm 4f136s2 4f12 88
Yb 4f146s2 4f13 86.8
Lu 4f145d16s2 4f14 86.1
Consequences of Lanthanide Contraction
Properties of Lanthanide

Magnetic properties

La3+ (4f0) and Lu3+ (4f14), having no unpaired electron; these do not show
paramagnetism while all other tri positive ions of lanthanides are paramagnetic.

Complexes

Although the lanthanide ions have a high charge (+3), their large size (0.85 – 1.03
Angstrom) imparts them low charges density (charge to size ratio) with the result
they cannot cause much polarisation and hence do not have much tendency to
form complexes. Their complexes with unidentate ligands like β-diketones, oximes
and ethylene diamine tetra-acetate (EDTA) are fairly common.
Color in lanthanide

Color due to f to f transition. The lanthanide metals are silvery white. The trivalent
lanthanide ions are colored both in the solid state and in aqueous solution. The
colours are unchanged even on alteration of the anions indicating that they are
characteristic of the cations.

Approximate colors of lanthanide ions in aqueous solution

Oxid
ation 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
state
+2 Sm2+ Eu2+ Tm2+ Yb2+
+3 La3+ Ce3+ Pr3+ Nd3+ Pm3+ Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+ Yb3+ Lu3+
+4 Ce4+ Pr4+ Nd4+ Tb4+ Dy4+
Antenna effect
• Weak light absorption by forbidden f-f transitions; molar absorption
coefficients ε are < 10 mol L-1 cm-1.

• Indirect excitation via attached ligands or via host lattice in order to get
sensitized luminescence.

• Excitation energy is transferred from ligand to lanthanide ion.


Antenna effect

A = absorption, F = fluorescence, P = phosphorescence,


L = lanthanide-centered luminescence, ISC = intersystem crossing,
ET = energy transfer; S = singlet, T = triplet.
Inorganic sensitizer

• Sensitization is not only possible via energy transfer from triplet state of organic
ligands, but also by:
–Inorganic chromophores (e.g. MoO42-, VO42-)

Lanthanide phosphors
White light production

There are three “prime” colors corresponding to the three spectral responses of human vision

Color rendering index obtained by mixing the three prime colors


Lamp phosphors

compact
fluorescent
lamp (CFL)
Security inks

Euro bills
Security inks

Under UV irradiation
Eu3+: red luminescence
Tb3+: green-yellow luminescence
Lewis Acids and Bases

Dr. Chandrakumar Appayee


Assistant Professor
IIT Gandhinagar

https://achandra9.wixsite.com/ch-201
Characteristics of Lewis acids
Interpretation of hardness
Hard acid–base interactions are predominantly electrostatic; soft acid–base interactions
are predominantly covalent.

The classification of Lewis acids and bases*

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