lecture 5 oms
TRANSCRIPT
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Lecture V.
. Organic Conductors Charge-transfer Complexes and Radical-ion Salts Other Low-dimensional materials Polymers
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•Conductive organic molecules
•“Plastic can indeed, under certain circumstances, be made to behave
very like a metal - a discovery for which Alan J. Heeger, Alan G.
MacDiarmid and Hideki Shirakawa are to receive the Nobel Prize in
Chemistry 2000”.
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•Molecular building blocks Single bond:
sp3
hybridization
Double bond:
sp2 hybridization
•p-AO o f neighborng i caronb
atoms form π-bonding
•Rigid bond, length of 134 pm
Carbon atom can form
four σ-bonds.
Free rotation is possible
with activaton i energy of 0.1
eV.
Bond length 154 pm
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•Molecular building blocks
Cyclic polyenes with conjugation
•that spreads the entire ring are
•called aromatic or arenes
Stability and delocalization of π- •electrons maintained in fused
•rings (polycyclic aromatic molecules)
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•Molecular building blocks
Molecules with more than one
double bond called polyenes.
Shape and properties of the
molecule depend on the position of
the double bond
Conjugated double bonds play a
particular role as π-electrones are
delocalized over the extent of the
conjugation
Isolated double bonds
Conjugated double bonds
Cumulated double bonds
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•Molecular building blocks Molecules with smaller or larger rings or other atoms in the
•ring (heterocycles) possess the same delocalization
•properties if the number of π-electrons is six.
•Cyclopentadiene anion
•Cycloheptatriene cation
•Heterocycles
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•Molecular building blocks
Molecules with a triple bond
are called alkynes
Here, the π-electrons form a
cylindrical cloud around σ-
bond
Very rigid, linear bond with
the length of 120 nm
Conjugated triple bonds
show the same
delocalization as double
bonds
Acetlene y
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•Molecular wires Molecular wires are, generally, rod-like structures with delocalized p-system,
•the longer the structure the lesser the difference between the frontier orbitals
•and the Fermi level of the electrode
polyene – alternating system of single
and double bonds;
polythiophene
polyphenylenevinylene
polyphenyleneethynylene
thyophenylsubstituted benzene
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Conductivity Of Organic Materials
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There are Thermally-stable Good Insulators
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We will concentrate on the good conductors
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Charge Transfer Complexes
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Radical-Ion Salts
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Discovery of Conducting Organic Crystals
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TTF-TCNQ
Uniform segregated stacks (1D system) Metallic conductivity Metal-insulator transition at TMI = 54 K
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TTF-TCNQ ANALOGS
S
S
S
S
Se
Se
Se
Se
Se
Se
Se
Se
TSFHMTTF HMTSF
HMTTF-TCNQ TMI = 48, 43 K 2.38a x 2.78b x c r = 0.72
HMTSF-TCNQ T = 24 K Toward semi-metal a x 2.7b x c with r = 0.74
TSF-TCNQ : TMI = 29 K 2a x 3.15 b x c r = 0.63
TCNQ is not necessary ! Cation radical salts with spectator anions (Brˉ, BF4ˉ, ClO4ˉ, PF6ˉ, …) obtained by chemical (Br2, I2, …) or electrochemical oxidation (electrocristallization)
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Other Low Dimensional Materials
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Conductivity is controlled by the phthalocyanine ring. The metal core does not interfere the conductivity.
Phthalocyanine channel
I-
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Chain length: Si:12030 Ge: 7440 Sn:10040
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Polymers
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Insulating Polymeric Donor Molecules
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Some Chemical Types of Polymers
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Conjugated Polymers
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Polyacetylene
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Electrical conductivity of polyacetylene
Cis-PA s = 1.7 x 10-9 S/cm Trans-PA s = 4.4 x 10-5 S/cm I2 doped s = 5.5 x 102 S/cm AsF5 doped s = 1.2 x 103 S/cm Electrochemical Oxidation s = 1 x 103 S/cm Li doped s = 2 x 102 S/cm Na doped s = 101-10-2 S/cm
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Polyparaphenylene (PPP)
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Polyaniline (PANI)
Conductor
Insulator
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Conductivity Of Organic Materials
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