Inorganic Chemistry
Cheesman
Contents
Mononuclear Magnetic
Crystal Field Theory
Dinuclear
Polynuclar
Extended Structures
Mononuclear Electronic
Mononuclear Electronic
Mononuclear Complexes | Electronic
s, p, d, f wave functions result from Schrdinger's equation for Hydrogen atom
He onwards is complicated due to electron-electron repulsion
Use hydrogen orbitals as a basis set
The electronic configuration (d3)
How many electrons are in the d-shell that can be arranged in multiple ways in the
d-orbitals
Orbital Angular Momentum
Angular momentum properties for single orbital wave functions
s
ml
+1, 0, -1
+2, +1, 0, -1, -2
Etc
Mononuclear Electronic
Free Transition Metal Ion (no ligands, spherical symmetry)
Total orbital angular momentum (L)
Derived from arrangement of the spins of the individual electrons
Due to the valence electrons
Filled subshells dont contribute as they have total angular momenta of L=0 and S=0
Term Symbols
Energy levels are labelled using term symbols showing values of L and S
Needed to explain spectroscopic and magnetic properties
(2S+1)L
Example
L = 3 and S = 3/2
4F
Mononuclear Electronic
Total spin angular momentum (S)
Identifying the Term Symbols
Takes Spin and Orbital Angular Momentum of single electron
s1 2S, d1 2D
Multiple Electrons
Identify all possible arrangements, microstates, of electrons using pauli
exclusion principle
Adding the ml and ms of each state to give total ML and Ms
Groups of degenerate microstates represent the components of that term
Identify the highest value of ML
This must have MS = 0 and will group with other ML values Ms = 0 to give
term 1L (grey)
The next highest ML will have more than one microstate with different
spins. These will give 3(L-1) states etc..
Mononuclear Electronic
Single Electron
Identifying the Ground Term
S has the highest value allowed by Pauli,
Then, L has the highest possible value
Quick Method
Draw 5 d orbitals, labelled with ml values and feed in
electrons +2 onwards
Add up ml values to give (+)2 = L=2 = D
Add up spins of 4 electrons: 4 x (+)1/2 = S=2 = 2S+1 = 5
Ground term is 5D
Mononuclear Electronic
Hunds Rule | The most stable term is predicted by
What are the ground terms for
V3+
3F
Cr3+
4F
Cr2+
5D
Ni2+
3F
How many states are within each of
these terms
1G
3F
21
1D
3P
1S
Work out degeneracy of L (2L+1)
Work out degeneracy of S (2S + 1)
Multiply together to get total number of states
Contents
Mononuclear Magnetic
Crystal Field Theory
Dinuclear
Polynuclear
Extended Structures
Mononuclear Magnetic
Mononuclear Electronic
Magnetic Properties | Electron
=
( + 1)
Magnetic Moment
Combination of s and the charge (-e)
gives the electron a magnetic
moment
The Zeeman Interaction
Magnetic moment of electron has
different energies when aligned with
or against a magnetic field
Magnitude of Zeeman Splitting
For 1 Tesla magnetic field
= 1.8 1023
= 1 1 ()
Mononuclear Magnetic
Spin Angular Momentum s
Magnetic Properties | Electron
Sample containing molecules with one unpaired electron in magnetic field
Thermal equilibrium between +1/2 and -1/2 states
Magnetic moment is cancelled out
Only slight excess in ground state leads to magnetisation M
Net bulk magnetisation is derived from measurements of magnetic susceptibility X
Use a faraday balance
Mononuclear Magnetic
Temperature Dependence
Magnetic Properties | Electron
M or X are linearly proportional to temperature at high temperature
Curie region at low 1/T
Many PARAMAGNETS obey the Curie Law
Often get better fit using Curie-Weiss
is the Weiss constant
Mononuclear Magnetic
Curie Temperature
Measuring Magnetic Properties
Traditional Methods
Faraday balance
Gouy balance
Modern Method
SuperConducting Quantum Interface
Device (SQUID)
Mononuclear Magnetic
Measuring Magnetic Properties
Boltzmann population differences
increase in higher magnetic fields
This leads to a lower total energy
A paramagnet is pulled into regions
of higher magnetic field intensity
Extracting from
A raw measurement of paramagnetism via will display a strong temperature
dependence
We are interested in the magnetic moment of the individual paramagnetic
transition ion
This will tell us how many unpaired electrons are present
is obtained from by removing the effect of temperature
At high temperatures the magnetic susceptibility is proportional to 1/T in the
curie region
Magnetic moment can be obtained from the equation
3
=
0 2
= . ()
The magnetic moment is usually called the effective magnetic moment
Mononuclear Magnetic
Magnetic Moment arises from both S & L
Magnetism does not just contain spin of single electron (S=1/2) but also L.
L results from the freedom of electron to move between orbitals and rotate
around the nucleus
For free ions, the quantum numbers L and S are known from the term symbol
Van Vlecks equation:
Mononuclear Magnetic
Symmetry-Quenched Magnetic Moments
Sometimes the magnetic moments observed are lower than those of the free
ion
This is because we assume that L = 0 and the Van Vlecks formula reduces to
the spin only formula
= 2 (( + 1)
Example
K3Mn(CN)6 = 4.81
Mononuclear Magnetic
Example
K3FeF6 =5.90 B
K3MnOx3 Spin-only
Mononuclear Magnetic
Example
Contents
Mononuclear Magnetic
Crystal Field Theory
Dinuclear
Polynuclear
Extended Structures
Crystal Field Theory
Mononuclear Electronic
Crystal Field Theory
Each ligand is a point electronic charge bound to the metal cation
Effect on energy with relative d orbital
ML6
1.
Surround metal with spherical shell of negative charge (barycentre)
2.
Localise charge to six point charges
3.
The dz2 and dx2-y2 will raise in energy as they are repelled more along the axis
4.
The dxy, dyz, dzx orbitals drop in energy as they are inbetween the axis
Crystal Field Theory
LFSE
For octahedral
LFSE = [(0.4 x t2g electrons) (0.6 x eg electrons) ] + P
P = extra pairing energy compared to if it was not in a ligand field (5 degenerate orbitals)
4
For tetrahedral = 9
LFSE = [(0.6 x t2g electrons) (0.4 x eg electrons) ] + P
Crystal Field Theory
Spectrochemical Series
High Spin
High Spin
Low Spin
Halogens
Sulphur
Oxygen
Nitrogen
Carbonyls
Carbonyls
Amines
Phosphines
I - < Br - < S 2- <
SCN - < Cl - <
NO3 - < F -
< HO - < C2O4 2< H2O -
< NCS < CH3CN <
NH3 < en < bipy
< phen < NO2 - <
PPh3 < CN - < CO
Increases with oxidation state
Higher charge smaller ion shorter M-L
Increases going down a group
Expanded 4d and 5d = better M-L bonding
Low Spin
Strong Field
Large
Crystal Field Theory
High Spin
Weak Field
Small
Molecular Orbital Theory
Molecular Orbital Theory
Orbital Overlap
A bond can only be formed when two atomic orbitals of two atoms overlap
Orbitals must be of similar energy
To simplify the theory in our context, the 4s and 4p orbitals on the metal atom
are ignored.
Recall the different types of donor/acceptor behaviour
Sigma Donor
Ligands point along axis
Example, Cl-
Sigma Donor
For the Cl- ion:
Electrons are in a p-orbital
Can be donated to form a sigma bond by overlapping with eg orbitals
Metal based eg raised in energy
No net overlap with t2g
Hence energy of t2g unchanged
Sigma Donor
Molecular Orbital Diagram
Effect of Sigma Donation
What happens as strength of sigma donation increases?
Energy of interaction increases
Splitting between the bonding and anti-bonding orbitals gets larger
eg moves higher in energy
Ligand field splitting (o) increases
Pi donor
Certain p-orbitals can interact with
t2g to give pi bonds
Overlap is possible
Example ClNo net overlap with eg sets
Pi donor
Molecular Orbital Diagram
Effect of Pi Donation
What happens when Pi Donor interactions increases?
Energy of inter-actions increases
Splitting between bonding and anti-bonding orbitals increases
t2g moves higher in energy
Ligand field splitting (o) decreases
Complete Molecular Orbital Diagram
Combination of sigma and pi donor interactions
Pi acceptor
Metal orbitals involved are the same as pi donor
Symmetry of atomic orbital overlap determines sigma or pi interaction
Only interacts with t2g
Pi acceptor
Requirements
Ligand must have an empty or partially filled orbital of pi symmetry
Accepting electron density
Typically anti-bonding orbitals
Results in Back Donation
Examples, CO and CN-
Pi acceptor
Molecular Orbital
Diagram
Pi acceptors increases o
Electronic Spectra
Place terms on a diagram to work out transitions
As octahedral ligand field is imposed, terms split and move further apart as ligand
strength increases
Distances between lines is proportional to energy not intensity
Orgel Diagram
Tanabe-Sugano Diagram
Lowest line is ground state
Related to a Racah parameter
Same spin multiplicity as ground state
are allowed
Ground state runs along the x-axis
Crystal Field Theory
Selection Rules
More allowed transitions have greater intensities not energies!
= 1
= 0
For d-d transitions all should be weak due to L rule but d orbitals not purely d for
non hydrogen atom due to mixing of orbitals with p.
Laporte rule (g g and u u forbidden) But u g Allowed
Therefore t2g eg Forbidden (octahedral)
t2 e allowed (tetrahedral)
Numbers
Transition Type
Typical epsilon (M-1 cm-1)
Pi Pi*
10,000 100,000
CT
10,000 100,000
Spin allowed, Laporte Allowed
500
Spin allowed, Laporte Forbidden
10
Spin Forbidden, Laporte Forbidden
0.1
Crystal Field Theory
Contents
Mononuclear Electronic
Crystal Field Theory
Dinuclear
Polynuclear
Extended Structures
Dinuclear
Mononuclear Magnetic
Cages and Clusters
Cages ( M L M)
Super exchange via ligands and magnetism
Copper acetate nonohydrate
Cluster (M M )
Multiple bonds and molecular orbitals
Chromium acetate nonohydrate
Cu-Cu 2.64 A (longer than 2.56 A in metallic copper)
Dinuclear
Cages
Copper acetate nonohydrate
Cages
Copper acetate nonohydrate
Magnetic susceptibility X drops
at low temperatures
Becomes diamagnetic < 77 K
Room temperature EPR signal
EPR disappears < 77 K
Dinuclear
Unpaired electron in singly
degenerate orbital
Coupling of spins
Coupling of spins
S1 + S2 to give maximum spin
S1 S2 to give minimum spin
Dinuclear
Every other spin state =
subtracting 1 from maximum
until you reach minimum
J is positive for ferromagnetic
coupling
J is negative for
antiferromagnetic coupling
Copper acetate
For copper acetate
S1 =
S2 =
S = 1 or 0
Drop temperature, bottom level is filled more than top
Hence Cu acetate is antiferromagnetic due to RT EPR
spectrum
Cages
Magnetic Exchange
Ligand mediated coupling is super
exchange
Spin polarisation across the three atoms
favours pairing of spins, leads to
antiferromagnetic coupling (with
exceptions)
Ferromagnetic coupling requires
orthogonality in coupling pathway.
High symmetry required and is rare
Dinuclear
Nature of M M interaction is through
the ligand
Clusters
Chromium acetate nonohydrate
Evidence for M M
Cr Cr = 2.36 A (shorter than that found in metal 2.58 A)
Eclipsed structures and possible formation of quadruple bonds
Short bond lengths (bond length increases with higher bond order)
Short bond lengths have higher vibrational frequencies
Dinuclear
Evidence for M - M
Overlap of d orbitals in M2 fragment
Dinuclear
Overlap of d orbitals in M2 fragment
Staggered
Eclipsed
3.5 also Eclipsed
Staggered
Dinuclear
d/d* orbitals can
only exist when the
molecule has
elipsed alignment.
The formation of
the d/d* orbitals
rests the complex
better than it being
staggered due to
steric strain
Evidence of d-bond
Dinuclear
Valence Delocalised
When you reduce this CuA species by one electron, the
electron. It is shared
CuII CuII Cu1.5 Cu1.5
The MO is delocalised across both copper ions.
Transitions can occur from this MO to higher antibonding
Mos and this transition can be intense (CuA is
blue/purple)
Valence Trapped
Prussian Blue KFeIII[FeII(CN)6]
Inter Valence Charge Transfer Band
Distinct ligand environments lock oxidation states in place
Reduction of FeIII to FeII is colourless
pi system of cyanide cruicial for charge transfer process
Similar IVCT bands from low level iron in brown glass and
brown sandstone
Dinuclear
Valence Trapped (More Examples)
Corrundum (Crystalline Al2O3)
Little titanium = colourless
Little iron = very pale yellow
Both Ti and Fe = Intense blue sapphire
IVCT band of Fe2+ Ti4+ transition
Oxidation states briefly altered while the molecule is in
the excited state
Intermediate Behaviour
Creutz-Taube ion
Any degree of valence trapping e.g. Ru2.4+ Ru2.6+ leads to
slightly different bond lengths
Franck-Condon: electron jump instantanoues
Then ligand environment relaxes
Transition is IVCT like but bond lengths are optimised
shortly after oxidation
Dinuclear
Strength of Electronic Interactions
Dinuclear
Contents
Mononuclear Electronic
Crystal Field Theory
Dinuclear
Polynuclear
Extended Structures
Polynuclear
Mononuclear Magnetic
Trinuclear Same properties as dimers
Cages M L - M
Copper acetate behaviour [Cr3O(O2CC6H5)6(py)3]ClO4
Even though each interaction is antiferromagnetic due to superexchange,
the moments on each three centres can not be cancelled
Spin states couple in the same way
Couple S1 with S2
Couple each state with S3
Clusters M M
Chromium acetate behaviour Cs3[Re3Cl12]
Has Re-Re double bonds
Lower Halides
Early block transition metals in low oxidation
states
No M-M bonds ever seen for > (VI) due to d-orbital
contraction
High order M-M bonds encountered
Steric effects compete with electronic
<18 electron complexes often seen
Polynuclear
SPIN FRUSTRATION
18 electron counting
3-
Re (group 7)
3 x terminal Cl-
share of 2 x bridging Cl-
2 x double bonds
net charge
Total
18
Polynuclear
Re
18 electron counting on dimers
[Re2Cl8]2-
[Mo2Cl8]4-
[W2Cl9]3-
Mo (group 6)
W (group 6)
4 x terminal Cl-
4 x terminal Cl-
3 x terminal Cl-
quadruple bond
quadruple bond
3 x bridging Cl
net charge
net charge
triple bond
Total
Charge
16
Total
4
3
16
Total
18
18 electron rule not as uniformly obeyed for d block as you go down group
d d bonds are general feature of early d-block elements in low oxidation
states
These tend to follow 18 electron rule, especially carbonyls
Polynuclear
Re
Carbonyl Clusters
Polynuclear
Carbon Monoxide
Polynuclear
Neutral ligand with small dipole
Weak 2 electron sigma donor
An extremely good pi acceptor
Nitric Oxide NO
Pi acceptor ligand strengths
CN - < NN < CO < NO+ (isoelectronic)
Some complexes better describe it as NO or even NO (nitroxyl)
This is bent (120 135 O)
Do not need linear for pi overlap
No analogous behaviour to CO
Polynuclear
Normally NO written as NO+ as a 3 electron donor
Anti bonding pi electron transferred to metal giving a NO+ (nitrosonium ion) ligand
This is a two electron sigma donor analogous to CO
It is approximately linear (160 180 O)
The odd electron is removed from anti bonding orbital, the stretching frequency is
usually similar or greater than NO itself
Due to charge NO+ is much better pi acceptor ligand showing better levels of back
bonding
Nitric Oxide NO
Polynuclear
Large Clusters Wades Rules
As cluster size increase, 18 electron rule fails
Polynuclear
Large Clusters Wades Rules
As cluster size increase, 18 electron rule fails
Rh6(CO)16
Os6(CO)18
54
6 x Os
48
16 x CO
32
16 x CO
36
TOTAL ELECTRONS
86
TOTAL ELECTRONS
84
Use 6 orbitals per metal
for M-CO bonds
Electrons left for
bonding framework
Electron Pairs
- 72
Use 6 orbitals per metal
for M-CO bonds
14
(n+1) with n = 6
Octahedron
But octahedral edges arent bonds
Did not actually have 3 CO per metal
Electrons left for
bonding framework
Electron Pairs
- 72
12
(n+1) with n = 5
Capped Trigonal Bipyramid
These rules compare it to the points of an octahedron
Polynuclear
6 x Rh
Contents
Mononuclear Magnetic
Crystal Field Theory
Dinuclear
Polynuclear
Extended Structures
Extended Structures
Mononuclear Electronic
Paramagnets
Drop in temperature increases magnetisation due to
population of states etc etc etc
Curie temperature and that shit (go back to slide 12)
NO INTERACTION ON SPIN BETWEEN DIFFERENT MOLECULES
Interaction tending to align the spins
As T drops, X increases more rapidly than expected due to
the spin-spin interaction
The curie temperature thermal randomisation is overcome
and all the spins align, sample has net magnetisation
Ferromagnets
Antiferromagnets
Interaction tending to align neighbouring spins antiparralel
As T drops, X decreases more rapidly than expected.
Neel temperature thermal randomisation overcome by coupling and
the spins lock down onto the two interpenetrating sublattices with
antiparralel allignments
Usually result of superexchange
Extended Structures
Ferrimagnets
Subclass of antiferromagnets
Moments do not cancel due to differences in spin
Large moment can persist below critical temperature (Curie temperature)
Fe3O4 Magnetite
Original ferrimagnet, can be permanently magnetised
Magnetised by earths magnetic field
Inverse spinel structure
Adopted by AB2O4 materials based on face-centred cubic structure of oxide ions
Extended Structures
Domains
Domain Boundaries
Magnetostatic Energy
Flux lines have a magnetostatic energy.
This can be reduced if the material is
divided into domains
Alligning ferromagnetically exchangecoupled spins in an antiparralel fashion
is not the most stable arrangement. But
the dominant term is the magnetostatic
energy and creates the formation of
domains.
Domain boundaries vary in size
normally a few hundred atoms. The
manner in which spin orientation
changes also varies
Magnetocrystalline
Energy
Dipoles in domains will tend to align
one of the easy directions wrt the
lattice
Extended Structures
Ferromagnetic materials, block
material, large magnetic moment
Hysteresis
Extended Structures
Applying a magnetic field in a closed domain structure, returning the field to non
zero, and then increasing the field in the opposite direction.
Magnetic Field Scan| Paramagnet
Hysteresis Loop | Ferromagnets
Below the curie temperature, the magnetic
field scan of a ferrimagnet results in a lag of
magnetisation (hysteresis)
First ramp is paramagnetic behaviour
Saturation Magnetisation : Maximum
magnetisation
Remanence Magnetisation : Amount of
magnetisation left when B = 0
Coercive field : value of B in opposite direction
to demagnetise the sample
Extended Structures
Forward and reverse scan on paramagnetic molecules, trace is reversible.
The remnant magnetisation is zero
Single Molecular Magnets & Single Chain Magnets
For a paramagnet the spins are independent of one another and no molecule
is locked into one of the + or - states (dynamic equilibrium)
For ferromagnets and ferrimagnets below their critical temperature, the
domains can be locked into one orientation, and thermal energy is insufficient
to randomise them.
The critical property is inertia, an energy barrier, the reorientation of a large
magnetisation at a particular temperature.
Ferromagnetic Strategy
Ferromagnetic coupling can only
occur if coupling is absolutely
orthogonal
The oxalate ion can do this
complex as ligand strategy to
create polynuclear structures
This results in a large ground state
spin which can interact within the
extended solid
Extended Structures
Single Chain Magnet
Example of Ferrimagnetic strategy to produce large spins
Accepting the inevitability of antiferromagnetic ligand mediated coupling but using
alternating spins of very different magnitudes so as to maximise uncancelled net spin
Results in a large ladder of spin
states
Interactions between chains add
another level of complexity, can
be altered by adding
substituents to the bridging
ligands
Extended Structures
Single Molecule Magnet
Mn12 can be the smallest molecular magnet
Single chain magnets units with large spins, tetranuclear molecules and
extended chains. Exhibit molecular magnet behaviour, such as hysteresis, but
often have very low critical temperature.
Challenge is to raise this temperature
This compound has the specific structure to show non-paramagnetic behaviour
A molecule containing lots of Fe ions wont show hysteresis
MCD
4.2 K
1.7 K
Extended Structures
Electrical Conductivity
Conductivity
Ionic conduction can occur with ions, but we are only concerned with electrons and holes
Band Theory
Imagine an alkali metal (group 1 conductors)
In an extended array of solid each s AO contributes to a MO. The
number of AO you overlap must be the number of MO you get out.
Hence a band rather than discrete energy levels
Same applies to p and d orbitals
Extra MO only fills the current set, it does not raise and lower the
maximum and minimum levels
For alkali metal, there are N electrons and N orbitals
Each orbital takes 2 electrons
Therefore only lowest N/2 orbitals are filled.
Highest filled orbital is the Fermi Level
Extended Structures
= n e (number of current carrying species x electron charge x mobility
Band Theory
Extended Structures
Band Theory
Extended Structures
Band Theory
Extended Structures
One-dimensional solid
Extended Structures
Shows conductivity
Does not show
conductivity
Extended Structures
First row transition metals with rock salt
structure
