ELECTRONIC SPECTRA :

Warna & Kemagnetan Senyawa Kompleks

2017
Outline

 Definisi electronic spectra (spektra

elektronik)
 Teori transisi elektronik
 Teori yang menjelaskan electronic spectra :
warna senyawa kompleks
 Diagram Tanabe Tsugano
 Deret spektrokimia
 Kemagnetan seny. kompleks
 Moment magnetik seny. kompleks
UV/Vis Spectrum for [Co(NH3)6]Cl3
UV/Vis Spectrum for [CoCl(NH3)5]Cl2
UV/Vis Results
UV/Vis Results
 1
T1g←1A1g and 1T2g←1A1g

 [Co(NH3)6]Cl3
 Absorbs violet/blue, ends up being orange-yellow
 2 absorption bands, symmetrical, Oh

 [CoCl(NH3)5]Cl2
 Absorbs green, ends up being magenta
 2 absorption bands, broadening on one
 C4v symmetry
Teori senyawa koordinasi

 VBT : ikatan
 CFT : elektronik spektra : warna dan
kemagnetan (spektra UV dan Visible)
 MOT : ikatan
 LFT : elektronik spektra : warna dan
kemagnetan
Electronic Spectra

 Mempelajari tentang spektra senyawa

kompleks berdasarkan tingkat energi
elektron dari suatu orbital (spektra
elektronik)

--> Aplikasi : bonding dan structure

Spektra elektronik senyawa kompleks

 Absorpsi energi cahaya berada dalam daerah sinar

tampak oleh suatu senyawa ---->> spektrum visible
---->> warna

 Absorpsi mengakibatkan terjadinya transisi antara

tingkat energi elektronik (transisi elektronik)

Energi cahaya yang diserap oleh molekul

mengakibatkan transisi elektron ke tingkat energi yang
lebih tinggi setara (sama dengan) perbedaan energi
pada tingkat energi orbital
Warna senyawa kompleks
Teori Warna Komplementer
 Melibatkan serapan cahaya tampak.
 Warna yang tampak adalah warna komplemen
dari warna yang diserap.

Red light
transmitted

Blue light
absorbed

12
 Warna ion kompleks
 Warna yang tampak adalah komplemen dari
Warna yang diserap

Warna yg Warna
diserap tampak
Transition Electronic Theory

Theory to explain electronic

excitations/transitions observed for metal
complexes

 Teori yang menjelaskan tentang eksitasi yang

teramati pada sebuah senyawa kompleks
Teori Transisi elektronik
 Selection rules
(determine intensities)

Laporte rule
g  g forbidden (that is, d-d forbidden)
but g  u allowed (that is, d-p allowed)

Spin rule
Transitions between states of different multiplicities forbidden
Transitions between states of same multiplicities allowed
Since these selection rules must be strictly obeyed,
why do many d-block metal complexes exhibit ‘d–d’
bands in their electronic spectra?

These rules are relaxed by molecular vibrations, and spin-orbit coupling

Breakdown of selection rules
 Vibrounic Coupling
Spin-allowed ‘d–d’ transitions remain Laporte-forbidden and their
observation is explained by a mechanism called ‘vibronic coupling

An octahedral complex possesses a centre of symmetry, but

molecular vibrations result in its temporary loss. At an instant
when the molecule does not possess a centre of symmetry, mixing
of d and p orbitals can occur. Since the lifetime of the vibration
(1013 s) is longer than that of an electronic transition (1018 s), a ‘d–
d’ transition involving an orbital of mixed pd character can occur
although the absorption is still relatively weak
 In a molecule which is noncentrosymmetric
(e.g. tetrahedral), p–d mixing can occur to
a greater extent and so the probability of ‘d–d’
transitions is greater than in a
centrosymmetric complex. This leads to
tetrahedral complexes being more intensely
coloured than octahedral complexes.
 Spin Orbit Coupling :
A spin-forbidden transition becomes
‘allowed’ if, for example, a singlet state mixes
to some extent with a triplet state.

but for first row metals, the degree of mixing

is small and so bands associated with ‘spin-
forbidden’ transitions are very weak
Transisi elektronik : warna senyawa
kompleks
 Macam-macam transisi elektronik :
a. transisi dalam tingkat energi orbital d ion
logam (d-d ‘ transition)
b. Transisi antara ion logam dengan ligan dalam
orbital molekul (charge transfer)
- LMCT (ligand to metal CT)
- MLCT (metal to ligand CT)
Intensitas absorbsi oleh transisi CT lebih tinggi
dibandingkan transisi d-d’
Absorption bands in electronic spectra are usually
broad; the absorption of a photon of light occurs in
10-18 s whereas molecular vibrations and rotations
occur more slowly

Therefore, an electronic transition is a ‘snapshot’ of

a molecule in a particular vibrational and rotational
state, and it follows that the electronic spectrum will
record a range of energies corresponding to
different vibrational and rotational states.
 Elektronic spectra :
[Cr(NH3)6]3+
\
Theory supporting Electronic Spectra

CFT
LFT : MOT dan CFT
Teori Medan Kristal
 CFT : energi orbital d ion logam terpisah
(split) akibat adanya medan elektrostatik dari
ligan
 Crystal-Field Theory
Model explaining bonding for transition metal
complexes
 • Originally developed to explain properties for
crystalline material
 • Basic idea:
 Electrostatic interaction between lone-pair electrons result in
coordination.
 Energetics

 CFT - Electrostatic between metal ion and donor atom

i
i) Separate metal and ligand
high energy
ii) Coordinated Metal - ligand
stabilized ii
iii) Destabilization due to
ligand -d electron repulsion iv
iv) Splitting due to octahedral
field. iii
 Ligand-Metal Interaction
Crystal Field Theory - Describes bonding in Metal Complexes
Basic Assumption in CFT:
Electrostatic interaction between ligand and metal

d-orbitals align along the octahedral

axis will be affected the most.
More directly the ligand attacks the
metal orbital, the higher the the
energy of the d-orbital.
In an octahedral field the
degeneracy of the five d-orbitals is
lifted
d-Orbitals and Ligand Interaction
(Octahedral Field)

Ligands
approach metal

d-orbitals pointing directly at axis are

affected most by electrostatic interaction

d-orbitals not pointing directly at axis are least

affected (stabilized) by electrostatic interaction
 Splitting of the d-Orbitals
 Octahedral field Splitting Pattern:

The energy gap is
referred to as
(10 Dq) , the
crystal field
splitting energy.

The dz2 and dx2-y2 orbitals lie on the same axes as negative charges.
Therefore, there is a large, unfavorable interaction between ligand (-) orbitals.
These orbitals form the degenerate high energy pair of energy levels.
The dxy , dyx and dxz orbitals bisect the negative charges.
Therefore, there is a smaller repulsion between ligand & metal for these
orbitals.
These orbitals form the degenerate low energy set of energy levels.
 Magnitude of CF Splitting ( or 10Dq)
 Color of the Complex depends on magnitude of 
 1. Metal: Larger metal  larger 
 Higher Oxidation State  larger 
 2. Ligand: Spectrochemical series
 Cl- < F- < H2O < NH3 < en < NO2- < (N-bonded) < CN-
 Weak field Ligand: Low electrostatic interaction: small CF splitting.
 High field Ligand: High electrostatic interaction: large CF splitting.

Spectrochemical series: Increasing 

 Electron Configuration in Octahedral

Field
 Electron configuration of metal ion:
s-electrons are lost first.
 Ti3+ is a d1, V3+ is d2 , and Cr3+ is d3
 Hund's rule:
 First three electrons are in separate
d orbitals with their spins parallel.
 Fourth e- has choice:
 Higher orbital if  is small; High
spin
 Lower orbital if  is large: Low
spin.
 Weak field ligands
 Small  , High spin complex
 Strong field Ligands
 Large  , Low spin complex
 High Spin Vs. Low Spin (d1 to d10)
Electron Configuration for Octahedral complexes of metal ion having d1 to
d10 configuration [M(H2O)6]+n.
Only the d4 through d7 cases have both high-spin and low spin configuration.

Electron configurations
for octahedral
complexes of metal ions
having from d1 to d10
configurations. Only
the d4 through d7 cases
have both high-spin and
low-spin configurations.
Color Absorption of Co3+ Complexes
 The Colors of Some Complexes of the Co3+ Ion

Complex Ion Wavelength of Color of Light Color of Complex

light absorbed Absorbed
[CoF6] 3+ 700 (nm) Red Green
[Co(C2O4)3] 3+ 600, 420 Yellow, violet Dark green
[Co(H2O)6] 3+ 600, 400 Yellow, violet Blue-green
[Co(NH3)6] 3+ 475, 340 Blue, violet Yellow-orange
[Co(en)3] 3+ 470, 340 Blue, ultraviolet Yellow-orange
[Co(CN)6] 3+ 310 Ultraviolet Pale Yellow
The complex with fluoride ion, [CoF6]3+ , is high spin and has one absorption band.
The other complexes are low spin and have two absorption bands. In all but one
case, one of these absorptionsis in the visible region of the spectrum. The
wavelengths refer to the center of that absorption band.
Hubungan antara warna dan kekuatan
medan kristal
 Warna seny. kompleks berkaitan dengan
adanya transisi elektron antar sub level
orbital d yang terpisah (split)

 Panjang gelombang pada serapan maks seny.

komplek dapat digunakan untuk menghitung
energi pemisahan antar sub level orbital d
yang terpisah
Ephoton = hn = hc/l = D
 Hubungan antara warna dan kekuatan
medan kristal
 Absorpsi radiasi UV-visible radiation oleh
atom, ion, molekul:
 Terjadi jika radiasi memiliki energi yang sama yang
dibutuhkan oleh atom, ion, molekul untuk eksitasi
elektron dari ground state ke excited state.

green light
white red light
observed
light absorbed
Quantum-mechanical
description
 Absorption of light may occur
when the frequency of the
incoming photon, multiplied by
the Plank constant, is equal to the
difference in energy between
these two levels.

45
Spektra Elektronik [Cu(H2O)6]2+
Example:

 5 1014
Ion cupric hidrat menyerap foton pada frekuensi Hz or 600
2+
nm. Cu[H 2O]6

2+
Cu[H 2 O]6
 Energi yang melibatkan transisi elektron pada ion adalah
E  h  (6.63 10 34 J s)(5 1014 s -1 )  3 10 -19 J

 Dapat dikatakan bahwa ion (Cu(H2O)6)2+ berwarna biru maka ini

berarti ion menyerap foton pada panjang gelombang 600 nm
(oranye) sehingga memberikan warna biru pada mata kita

46
 3+
Ti[H 2 O] 6
Example

3+
 Ti1 memiliki konfigurasi 4s 2 3d, 2 sehingga ion Ti menjadi
d ion. Ini berarti pada groundstate, 1 elektron akan menempati level
energi terendah pada d orbitals, sedangkan level energi yang lebih
tinggi kosong, setelah menyerap foton dengan energi tertentu, level
energi terendah pada d orbitals akan kosong.

48
 3+
Ti[H 2O]ion
6 absorbs light in the visible region; the wavelenght corresponding
to maximum absorption is 498 nm.

                                                                                                
                                                  

Crystal field splitting :

hc (6.63 10 -34 Js)(3 108m/s)
  h    3.99 10 -19
J=240 kJ/mol
 498 10 m -9

Itu adalah energi yang dibutuhkan untuk mengeksitasisatu elektron pada

3+
ion Ti[H 2O]6
49
Spliting d-orbital sebesar 240 kJ per mol sesuai dengan panjang
gelombang cahaya warna blue-green ; absorpsi cahaya ini
mempromosikan elektron ke level energi yang lebih tinggi pada d
3+
orbitals, yang merepresentasikan keadaan tereksitasi dari kompleks Ti[H 2O]6
3+
Apabila kita melewatkan cahaya pada larutan Ti[H 2O]6 maka cahaya
warna blue-green akan diabsorb dan larutan akan menampakkan
warna violet .

50
 Spektra larutan [Ti(H2O)6 ]3+
 Serapan senyawa Co (III)

warna senyawa kompleks kobalt (III) dalam larutan air

dengan berbagai macam ligan

Kiri : weak-field ligand – serapan pada energi rendah -

λ warna merah - warna tampak : hijau
Kanan : strong-field ligan – serapan pada energi besar
- λ warna ungu - warna tampak : oranye/kuning
Faktor yang mempengaruhi warna

 Perbedaan warna disebabkan oleh perbedaan

besarnya 
▪  besar = energy untuk menyerap cahaya besar
▪ Panjang gelombang pendek
▪  kecil = energy untuk menyerap cahaya kecil
▪ Panjang gelombang panjang

 Besarnya  tergantung pada:

▪ ligand
▪ logam
Faktor yang mempengaruhi warna

 Logam
a. logam ukuran besar   besar

[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+

[Co(H2O)6]2+ [Cu(H2O)6]2+
b. biloks logam tinggi   besar

[V(H2O)6]
2+ [V(H2O)6]3+

Mn(II) Mn(VI) Mn(VII)

 DERET SPEKTROKIMIA

 Deret yang menyatakan urutan kekuatan ligan

berdasarkan besarnya ∆ yang dihasilkan
 Deret kekuatan ligan berdasarkan besarnya
∆o
 Deret kekuatan logam berdasarkan besarnya
∆o
Teori LFT

 Menggabungkan penjelasan tentang orbital

molekul dengan perbedaan tingkat energi
pemisahan orbital /splitting
Orbital molekul ML6 : s-orbital
Orbital molekul ML6 : p-orbital
Orbital molekul ML6 : d-orbital
Tipe ikatan logam-ligan
Splitting from  - bonding: Weak and Strong Field ligands
Contoh ligan Cl- (weak) danCN- (strong)

 - bonding as before
Cl M
Now  - bonding between p & dxy, dxz, dyz

sp hybridized for -bonding,

left over p orbitals make  and * orbitals

 - bonding as before
N  C N  MC *
Now  - bonding between CN- * & dxy, dxz, dyz
No  - bonding with CN- 
Ligan Phi-donor

 Ligan dengan orbital p terisi

Ligan Phi-donor
  - bonding: p orbitals give Weak Field Ligands (Cl- example)

Metal Molecule Ligand

Cl
Input d e-’s
p*
s* E (Cl- p) < E (M d) !!!
4p
d* = eg
4s *-antibonding orbitals
3d 12 Cl- p orbitals
dxy, dxz, dyz = t2g
           
-bonding orbitals 6 Ligands
Decrease oct Cl- sp orbitals

 Weak Field Ligand

     
6
Phi-akseptor

 Ligan yang memiliki orbital π * kosong

Phi-akseptor
Ligan Phi-akseptor
Orbital molekul CN-
  - bonding: * orbitals give Strong Field Ligands
N  C *

Metal Molecule Ligand

*- antibonding orbitals
12 CN- * orbitals
Input d e-’s p*
s*
4p E (CN- * ) > E (M d) !!!
d* = eg
4s
3d
dxy, dxz, dyz = t2g

6 Ligands
Increase oct -bonding orbitals CN- sp orbitals
 Strong Field Ligand
     
6
Molecular Orbital Theory Explains Field Strength of Ligands
1) Ligand p orbitals cause  - bonding that raises t2g energies
Weak Field Ligands
d* = eg
*
12 Cl- p orbitals
dxy, dxz, dyz = t2g

2) Ligand * orbitals cause  - bonding that lowers t2g energies

Strong Field Ligands 12 CN- * orbitals

d* = eg

dxy, dxz, dyz = t2g



3) sp3 hybridized ligands do not change t2g orbitals very much

No p or * orbitals for -bonding !!!
Medium Field Ligands
 Metal to ligand : M---L
Phi akseptor/phi acid

 Ligan to metal : L---M

phi donor/phi base
Faktor yang mempengaruhi warna

 Ligan
a. Weak field ligan
interaksi elektrostatik ligan dengan
logam rendah - ∆ kecil

b. Strong field ligan

interaksi elektrostatik ligan dengan logam
tinggi - ∆ besar
DIAGRAM TANABE SUGANO
Group theory analysis of term splitting
 Free ion
term for d2

3
F, 3P, 1G, 1D, 1S

Real complexes
Tanabe-Sugano diagrams

• show correlation of
spectroscopic transitions
observed for ideal Oh complexes
with electronic states
• energy axes are parameterized
in terms of Δo and the Racah
parameter (B) which measures
repulsion between terms of the
same multiplicity d2
d2 complex: Electronic transitions and spectra

only 2 of 3 predicted transitions

observed
 TS diagrams Other dn configurations

d3
d1 d9

d2 d8
 Other configurations

d3
The limit between
high spin and low spin
the spectra of dn hexaaqua complexes of 1st row TMs
 The d5 case

All possible transitions forbidden

Very weak signals, faint color
symmetry labels
 Charge transfer spectra
Metal character

LMCT

Ligand character

Ligand character

MLCT
Metal character

Much more intense bands

[Cr(NH3)6]3+
 Determining Do from spectra

d1
d9

One transition allowed of energy Do

 Determining Do from spectra
mixing

mixing

Lowest energy transition = Do

Ground state mixing

E (T1gA2g) - E (T1gT2g) = Do
 DERET SPEKTROKIMIA

 Ligan diklasifikasikan berdasarkan kemampuan

donor atau akseptor π

 Ligan dgn orbital p terisi----- π donor

Ligan dgn orbital π * atau d kosong ---- π akseptor
Deret Spektrokimia
Kemagnetan

 Kemagnetan senyawa kompleks

berhubungan dengan bagaimana elektron
terdistribusi pada orbital d.

 Kemagnetan senyawa kompleks diukur pada

suatu medan magnet.
 Senyawa kompleks dengan elektron tidak
berpasangan : menghasilkan medan magnet /
tertarik pada medan magnet.

 Senyawa kompleks dengan elektron

berpasangan : tidak menghasilkan medan
magnet / menolak medan magnet.
Ukuran kemagnetan

 Momen magnetik

Suatu ukuran yang berkaitan dengan jumlah

elektron tidak berpasangan.
 Moment magnetik :

Dimana :
 Dengan g = 2,0003 = 2 dalam Bohr magneton,
dan momentum orbital diabaikan, maka
 Dan S = n/2, maka momen magnetik :

 Satuan moment magnetik = BM (Bohr

Magneton)

1 BM = 9,27 x 10-24 Joule/Tesla

Latihan

1. Hitung moment magnetik komplek Cr(III)

dan Ti (III)
2. Moment magnetik Kompleks Co(II) adalah
4,0BM. Prediksikan konfigurasi elektron
orbital d pada kompleks tersebut!
3. Moment magnetik Kompleks Fe(III) adalah
5,3BM. Prediksikan konfigurasi elektron
orbital d pada kompleks tersebut!
 Jawab :
1. Cr3+
n=3
μs = √3(3+2) BM
= 3,87 BM
 Jawab :
3. Fe 3+ , n = 5
a. dihitung μs untuk kompleks high spin dan low
spin.
b. kemudian tentukan mana yang nilainya paling
mendekati nilai sebenarnya/eksperimen (5,3 BM)
c.kemudian tulis konfigurasi elektron high spin
atau low spin sesuai hasil b. Misal : untuk
jawaban highspin, maka konf elektronny t2g3eg2
4. Pada T = 298 K diketahui bahwa momen
magnetik kompleks [Cr(NH3)6]Cl2 adalah
4,85BM. Nyatakan apakah kompleks tersebut
high spin?
 TUGAS :
Baca buku Huhey, Douglas, dan buku teks
Anorganik lain yang menjelaskan tentang
spektra elektronik senyawa kompleks dan
kemagnetan

Silahkan berlatih menghitung momen

magnetik dari soal-soal yang ada di buku teks