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Charge Transfer Complexes

Charge-transfer complexes form through weak interactions between electron donors and acceptors without covalent bonding. They are stabilized by polarization and electrostatic attraction. Strong spectroscopic transitions in the visible/UV region occur due to charge transfer. These complexes have applications as organic semiconductors and in strengthening polyimides through tightly holding chains together.

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611 views26 pages

Charge Transfer Complexes

Charge-transfer complexes form through weak interactions between electron donors and acceptors without covalent bonding. They are stabilized by polarization and electrostatic attraction. Strong spectroscopic transitions in the visible/UV region occur due to charge transfer. These complexes have applications as organic semiconductors and in strengthening polyimides through tightly holding chains together.

Uploaded by

Jaba Priya
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Introduction

MO diagram
Electrical properties
CHARGE-TRANSFER COMPLEXES are defined as
those compounds which are formed by the interaction
of two molecules, ions or ionic molecular
combinations, to form complexes without covalent
bond participation.
Generally referred as Donor – Acceptor complexes
Basically, it is an acid – base interaction:
 Acid: electron deficient with vacant bonding orbital –
high electron affinity
 Base: electron rich with filled orbital – low ionization
energy
Electron donation – sigma nonbonding electrons
Electron acceptance – vacant sigma or pi orbitals

Stabilized by two factors:


 Polarization
 Electrostatic attraction

Although bonding is weak, a strong spectroscopic


electronic transition is observed in the visible / UV region –
CHARGE TRANSFER TRANSISTION
Metal to Ligand CT (MLCT)

Ligand to Metal CT (LMCT)


Predominates if complexes have

Ligands having low-lying *


orbital ( Aromatic ligands)

Metals ion has a low oxidation


number .
1
2

bpz: 2,2’-bipyrazine, [RuII(bpz)3]2+

bpy: 2,2’-bipyridine,

Absorption profile of the [RuII(bpz)3RuII(bipy)2Cl]3+ complex, in


aqueous solution, showing the MLCT bands of the [Ru II(bpz)3]2+ (1)
and [(bpz)Ru(bipy)Cl]+ (2) chomophores at 440 and 570 nm,
respectively
 Predominates if complexes
have Ligands with relatively
high energy lone pairs.
 Metals in high oxidation
state.
 These condition imply that
the acceptor level is available
& low in energy.
Examples Color of Transition

MnO4- Purple

Cds Yellow

HgS Red

Fe oxides Red & Yellow


L(t1) -> M(e) at 17700 cm-1 (565 nm)

L(t1) -> M(t2*) at 29500 cm-1 (340 nm)

L(t2) -> M(e) at 30300 cm-1 (330 nm)

L(t2) -> M(t2*) at 44400 cm-1 (225 nm)

Remember, visible light includes


wavelengths between ca. 400 and 750
nm, i.e. frequencies between 25000 and
13000 cm-1. This explains the deep
purple color of MnO4

MO diagram for MnO4-


Because of the non-stoichiometry of many of the
complexes studied electrically, their exact crystal
structure has not been clarified.
In some cases, where crystals of 1:1 complexes
are obtained, the donor and acceptor molecules
in  - molecular complexes are arranged in
alternating stacks.
Pyrene – pyromellitite
dianhydride complex:
Adjacent molecules
within a given stack –
completely
superimposed.
Hexamethylbenzene –
chloranil complex:
Off set arrangement
The formation of molecular CT complexes between donors and
acceptors plays an important role in many biological processes,
e.g. enzyme catalysis, drug action, and ion transfer through
lipophilic membranes.
 All involve complexation between two or more distinct molecules .

Also, it is possible that organic semiconductors of the CT type can


find application as cheap sources for the construction of organic
solar batteries in virtue of their semiconducting properties.
 Aromatic hydrocarbon form weakly interacting complexes with aromatic nitro compounds.
 Electrical resistivity ~ 1018 ohm cm

DONOR ACCEPTOR IGD AG A

Anthracene TNB 7.4 0.6


Phenanthracene TNB 7.85 0.6

Pyrene TNB 7.55 0.6


Perylene TNB 7.22 0.6
Anthanthrene TNB 7.01 0.6
Chrysene TNB 7.79 0.6
Aromatic hydrocarbon form such complexes as the
strength of electron acceptor is increased.

Example for typical acceptors are tetracyano ethylene


(TCNE) and poly haloquinones (chloranil)
DONOR ACCEPTOR IG D A GA p (ohm cm)2
Anthracene TCNE 7.4 1.9 1.1 x 1010
Perylene Chloranil 7.22 1.35 2.4 x 1012

Perylene Fluoranil 7.22 6x 1013

Phenanthracene TCNE 7.85 1.9 2 x 1014


Pyrene TCNE 7.55 1.9 4.5 x 1015
Pyrene Chloranil 7.55 1.35 1011
Hexamethyl Chloranil 7.55 1.35 1011
benzene
Similar to weakly interacting complexes, here also,
D and A are arranged in alternating stacks.

Steric effect will affect the extent of -electron


overlap between the two parallel molecular
planes.

D and A are more planar than in the first case, so


it facilitate the electron transfer from the donor to
the acceptor molecules.
Aromatic amines are good electron donors.
Fairly strong interaction between aromatic amines
and polyhalo quinones is predicted.
Complete electron transfer occur in the ground
state : ESR absorption due to formation of radical
ions D.+ A.-.
DONOR ACCEPTOR p (ohm cm)
N,N-Dimethylaniline Chloranil 4.3x 108
Bromanil 4.3x 108
Iodinal 8x 108
Aromatic hydrocarbon and halogen complexes.
A much closer approach between donor & acceptor
molecules.
Steric effects are minimal, so much closer interaction
between D and A is expected.
Such complexes are non-stoichiometric.
Electrical resistivity show strong dependence on the
halogen content.
Strong ESR signals due to strong CT interaction.
Activation energy for semiconductor & ESR signal were
identical over a specific range of temperature.
DONOR ACCEPTOR STOICHIOMETRY p (ohm cm)2

Perylene Bromine 1:2 7.8


Iodine 2:3 10.0
Pyranthrene Bromine 1:17 220
Iodine 1:2 17
Violanthrene Bromine 1:23 66
Iodine 1:2 45
Pyrene Iodine 1.2 75

Pyranthrene
Perylene Violanthrene
Semiconductor properties of CTC
based on the strong electron acceptor.
Form intermediate  charge-transfer
complexes with aromatic amines.
Anion radical of TNCQ can form a
no. of stable salt like derivatives with
various cations.
Unusual electrical & Magnetic
properties were observed.
π/π-Interactions can also lead to the formation or
conductive organic metals such as stacked TTF/TCNQ
CT complexes have been used as organic
semiconductors in field effect transistors (FETs),
charge injection and transport materials in
organic light-emitting diodes (OLEDs) and
organic photovoltaic (OPV) cells.
Polyimides have a great demand in the
industrial applications.
 This charge transfer complex holds the chains together very
tightly, not allowing them to move around very much.
 When things can't move around on the molecular level, they
can't move around in the whole material.
 This is why polyimides are so strong.
 This charge transfer complex holds the chains
together very tightly, not allowing them to move
around very much.
 When things can't move around on the molecular
level, they can't move around in the whole material.
 This is why polyimides are so strong.

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