Conjugated/Aromatic Systems – Special?

Conjugated Systems Aromatic Compounds

Field Effect Transistors

Pentacene

OLEDs

Kevlar Tamoxifen
Image source: Google Images (Anticancer drug)
 Part - I
Huckel Theory for Conjugated Systems

Acknowledgements
Prof. R.B. Sunoj, IIT Bombay
Prof. Pradeepkumar P. I., IIT Bombay
Prof. S. J. Gharpure, IIT Bombay
Prof. K. M. Muraleedharan, IIT Madras
 Learning Outcomes

At the end of this module you should be able to….

• Construct π – molecular orbitals for cyclic and acyclic molecules

• Explain the reactivity of molecules and reaction outcomes based on

MO Theory
 Molecular Orbital Theory
Molecular Bonds – formed when two atoms are brought from infinity close to
each other
Molecular orbitals - obtained by combining the atomic orbitals (AO) on the atoms
How do the AOs combine?
Think of the wave nature of electrons
MO2 Destructive (higher energy)

AO AO

MO1 Constructive (lower energy)

Energy
Orbital Mixing
 Types of Orbital Mixing
σ σ* Rows A & B
Axial overlap
σ MO
σ σ*

Row C
Lateral overlap
π MO
π π*
Column A Column B
Constructive Destructive
Bonding MO Antibonding MO
 More on σ Orbitals

• No nodes along the internuclear axis (Ignore AO nodes e.g. of p orbital)

• Symmetric along the axis

Questions??

8
Draw the MOs of Ethylene

9
 Types of Orbitals – Ethylene (C=C)

s*
Antibonding MO
ABMO
p*

Ignore C-H bonds p

Bonding MO
BMO
s

Huckel – The sigma framework can be neglected!!

 Ethylene – Simplified MO picture
The σ – framework neglected as it is in the nodal plane of the p atomic orbitals

Phase inversion
(node)

Qualitative Picture – Hückel’s MO

 Calculating Energies of MOs
Energy of each ith MO given by
EiMO = α + mjβ mj = 2 [Cos (jπ/n+1)]

Coulomb Resonance n = no: of carbon atoms

Integral Integral j = 1 to n

Coulomb integral – refers to energy of an electron in the field of its own nucleus , [can be
taken as valence state ionization potential]

Resonance integral - refers to energy of an electron in the field of the neighboring nucleus ,
[can be taken as the interaction between neighboring atomic orbitals]

Note: α and β are negative by definition

The α and β are not calculated as numerical values.
The energies are expressed in terms of these quantities