Beruflich Dokumente
Kultur Dokumente
00
,%8aXW
hS.S Led
Tetrahedron
Vol. 48.No. 48.pp. 10443-10514.1992
Printedin GreatBritain
SUPRAMOLECULAR PHOTOCHEMISTRY
Vincenzo Balzani
Dipartimento di Chimica Cl. Ciamician
Universid di Bologna, Bologna, Italy
Contents
1. Introduction
10444
2. Supramolecular Species
10445
10448
4. Cage-type Systems
4.1 Cage-type metal complexes
4.1 .l Cobalt complexes
4.1.2 Ruthenium complexes
4.1.3 Lanthanide complexes
4.2 Photo-cleavable and photo-flexible cages
4.3 Photochemistry of incarcerated molecules
10454
10454
10455
10458
10461
10464
10466
5. Host-Guest Systems
5.1 Polyammonium macrocyclic receptors with Co(CN)b35.2 Aromatic crown ethers with Pt(bpy)(NH,)z*+
5.3 Lasalocid A anion with Cr(bpy)s3+
10467
10468
10471
10477
10479
10488
7.1
7.2
7.3
10480
10483
10489
10490
10492
10493
10496
10496
10498
10502
8. Conclusion
10443
10444
V. BALZANI
1.
Photochemistry
is a natural
modern
of science,
branch
and
at
the
vision,
is
reproduction,
etc.)
and
and
suitable
rationalize
the
structural,
important
until
now
have
dealt
most
the
same
combination
knowledge
progress
new
way
as
on
molecular
materials
from
of
the
supramolecular
of
synthetic
(
e.g.,
4)
the
need
to
that
the
Up
investigations
to
chemical
supramolecular
trend:
1)
the
research
high
the
is
There
degree
of
extraordinary
continuous
small-upward
the
molecules,
species.
2)
3) the
fill
of
supramolecular
to
species;
for
to
molecules.
leads
leads
methods:
been
search
for
approach
gap
which
to
separates
biology.
most
species
processes
supramolecular
this
and
photochemistry).
atoms
shows
of
available
photochemical
to
reached
now
of
clearly
for
are
families
components
level
have
several
of
two
molecules,
properties
combination
reasons
by
organic
dynamic
(molecular
last
photochemical
complexes
species
molecular
the
and
fundamental
molecular
In
(image
remarkable
treatments
of
four
made
chemistry
variety
the
from
nanostructures);
One
of
literature
least
of
matter
biology.
technology
organometallic
states
Current
are
thousands
energetic,
molecular
moving
The
theoretical
of
rapidly
at
and
excited
with
species.
of
compounds,
most
efficacy.
(photosynthesis,
etc.).
a
and
and
and
life
to
reached
theoretical
elucidated,
as
photodegradation,
processes
coordination
well
to
world
light
physics,
importance
has
as the
between
chemistry,
as
photochemistry
photophysical
In
of
photocatalysis,
experimental
as old
at the interface
of paramount
phototaxis,
decades
phenomenon
crossroads
Photochemistry
Introduction
interesting
is their
that
aspects
interaction
may
ensue.
photochemistry.
of
the
with
light
This
is
chemistry
and
the
the
realm
of
great
of
.
In
the
last
few
years
Supramolecular photochemistry
supramolecular
photochemistry
several
directions.
are,
their
by
more
true
In this
together
with
own
nature,
review
emphasis
will
number
of discrete
by some
the four
type
types
and
derivatized
considered
laboratory,
relevant
definition
the
of
word
to which
will
have
been
components
can
not
be
other
deal
in Fig.
films,
in
some
discussed.
studied
held
we will
micelles.
from
systems
schematized
which
to split
the
in
liquid
way
be
Most
of
the
laboratories
1.
author
will
also
different
into
individual
as
According
1) or
systems,
from
such
are
individual
held
together
Fig.
The
components
Macrocyclic
1)
can
situation
are
kept
together
complexes
most
covalently-linked
of
(Fig.
their
but
clear,
1)
intrinsic
clearly
by
forces
where
for
where
and
subunits
the
catenanes,
(e.g.,
host-guest
supramolecular
systems
where
or covalent
metal
properties,
of separate
(e.g.,
defined
coordinative
identifiable
(components)
systems
however,
area
is the possibility
interlocked
be
the
distinguishes
modifications,
intermolecular
is less
on
subunits
concept,
straightforwardly
arbitrary
that
molecule
minor
molecules
by
feature
molecular
this
necessarily
depending
the
a large
or with
to
is
meanings
Conceptually,
capable,
components
species
species
species
system
existence.
maintain
have
it is applied.l-6
are
species.
Supramolecular
supramolecular
may
a supramolecular
Fig.
is even
considered.
Any
that
this
Specifically,
species
systems,
examples
2.
and
and
molecular
bond.
electrodes,
illustrated
but
along
chemistry
to supramolecular
semiconductors,
supramolecular
examples
areas,
be given
of supramolecular
crystals,
rapidly
photochemistry.
of chemical
polymers,
very
supramolecular
interdisciplinary
supramolecular
like
be
and
for
Systems
the
grown
Photochemistry
of a small
made
has
10445
ions
and
systems
(Fig.
the
bonds.
ligands
made
1) can
of
also
10446
V. BALZANI
0
cI.l
L
(i)
(ii)
(iii)
r-lB
l-lc
(4
Fig. 1.
Schematic
species:
representation
(i) cage-type
catenanes;
be
In
supramolecular
are
better
supramolecular
the
the
electronic
interaction
energy
relevant
energy
between
As
supramolecular
species
A-B
that
are
transfer
together
substantially
from
substantially
considered
a
as a large
and
the
A and
localized
delocalized
of
the
is small
Similary,
specific
leads
B,
When
A and
any
or
the
B,
the
components,
interaction
When
to other
defined
causes
an
excited
states
electron
states
species
and
of a
of bond
to excited
be
excitation
type
oxidation
substantially
and
units.
be
can
indicates
A or
of
compared
1, light
B subunits)
can
like
molecules
component
in Scheme
both
species
degree
system
on
molecule.
reduction
contrast,
large
the
viceversa).
on
species
on
subunits
(where
(iii)
molecules.
of
shown
A to B (or
supramolecular
oxidation
the
By
based
parameters,
species.
keeps
be
systems;
components.
between
subsystems
supramolecular
that
molecular
as large
can
of supramolecular
(ii) host-guest
distinction
species
types
species.
defined
the
practice,
between
systems;
(iv) covalently-linked
considered
fullerenes
of four
is
are
better
reduction
described
whereas
oxidation
of
as
Suprarnolecular photochemistry
Scheme
lo447
supramolecular
compound
large
species
molecule
*A-B
A-*B
hv
hv
c-------
A-B
t---
A-B
-ec-------
A-B
*(A-B)
A+-BA--B+
+e-
+eA--B
(A-B)-
A-B-
A+-B
-e-
(A-B)+
A-B+
and reduction
of a large
the
are
electron
(Scheme
principle,
supramolecular
isolated
the
to species
delocalized
properties
structure
components
however,
suitable
cies
substantially
leads
on
where
the
the hole
entire
or
system
1).
In
cases,
molecule
models
is not
species
species
connector
problem.
A
that
is
can
and
B would
never
bound
to
of real
are
be radicals
as such.
the
components
molecular
study
molecules.
components
some
via
species
cases,
the
constitute
and
speA-L-B
L
is
unsaturated
e.g.
carbon-carbon
such
several
in a covalent
or coordinatively
In
of
In
that
of
of a supramolecular
speaking,
active
the
molecules
components
Strictly
components
from
model
exist
since
molecular
obtained
identification
a trivial
A and
the
suitable
molecular
which
connector,
of
for
in
be
can
or
the
of
when
the
bonds,
as AH and BH or
10448
V. BALZANI
AR
and
BR
properties
(R=alkyl
to A and
however,
the
electronic
subsystem
compounds
that
be
to
used
may
indeed
of
include
the
active
the
more
such
of
In other
In
as A-L
properties
identical
deeply
components.
the connector,
approach
almost
species.
interact
Photochemical
act
of
any
and
and
photochemical
of a photon
that is formed
undergo
state
some
and
by a molecule
type of
case,
B-L,
B
molecule
reaction),
(ii)
in
the
processes
photophysical
(eq.
1). The
energy,
unstable
deactivation.7
can
and
emission
(iii)
occur
light
of
As
process
excited
species
shown
other
present
and
in the
of
(iv)
in
disappearance
is
state
which
Fig.
2,
excess
energy
type
(quenching
of
the
(photochemical
deactivation,
some
solution
(i)
products
(radiative
degradation
deactivation),
via
formation
of
(radiationless
species
should
(I)
deactivation
original
luminescence),
cases,
the
A + hv ----> *A
excited
in
with
such
and
photophysical
the absorption
must
be
species.
3.
first
will
B in the supramolecular
connector
supramolecular
The
group)
also
called
into
heat
of interaction
with
processes).
products
A + h$
/
*A
t
A+hJ
\
+B
A + heat
J
A and/or products
Fig. 2.
Light
excitation
electronically
of
excited
molecule
state.
and
deactivation
of
the
Supramolecular photochemistry
As
of
is well
light
known
from
absorption
absorption
(and
band)
is
thus
and
particularly
Transitions
from
the
value
are
transitions
and
allowed
to
can
excited
hardly
molecules
the
is a triplet
to
be
of
observed
ground
state
rise
in
the
can
be obtained
from
the
deactivation
this
reason,
least
three
states
excited
singlet
and
be directly
triplet)
are
as is shown
in the Jablonski
by
reaction
chemical
Emission
of
light
A@,)
is not
the
involved
number.
the
are
spectra.
by light
ground
of Fig.
represented
for
forbidden
In
most
excited
state
absorption
excited
states.
state
singlet
is
3, where
the
called
sake
of
fluorescence
AK+,)Fig. 3. Schematic
species.
energy
singlet,
kiscf
k,,
and excited
and ki,,
fluorescence,
crossing,
diagram
for
a typical
molecular
state
crossing,
level
state triplet,
respectively;
internal
conversion,
phosphorescence,
respectively.
and
rate
and
simplicity.
A(T, 1
abs
For
deactivation
kisc
but
process,
same
whereas
in a photochemical
diagram
states
bands,
lowest
of upper
(e.g.,
the
having
value
absorption
populated
(luminescence)
corresponding
of
intense
and
probability
quantum
spin
is a singlet
cannot
the
states
to
different
that
at
spin
to excited
give
states
of
the
characteristics
their
state
and
intensity
the
to
ground
spectroscopy,7
the
related
involved
spin
electronic
10449
excited
kr, kt,.
constants
for
S,PT,
intersystem
T,--+Su
intersystem
or
10450
V. BAUANI
phosphorescence
depending
on whether
same or different
spin compared
way, radiationless
deactivation
occurs
between
when it occurs
internal
states
to the ground
state
state.
is called internal
states
of different
are
conversion
and
conversion
the
when it
crossing
spin. Fluorescence
spin-allowed
intersystem
has
In the same
between
phosphorescence
the excited
steps,
crossing
are
and
whereas
spin-forbidden
steps.
Each intramolecular
constant
(Fig.
lifetime,
given by
decay
step is characterized
3) and each
excited
state
is characterized
z =l/Ziki
where ki
process
by its
(2)
is the first order rate constant for a generic
that
causes
the disappearance
unimolecular
of the excited
state.7
For
each process one can define the quantum yield, @, which is the ratio
between
the number
produced
and
absorbed.
For example,
yield
the
of moles
of emission
(phosphorescence
following
Op=q.
where
number
of moles
making
from
the
quantum
ISC
and z
Tl
of photons
reference
lowest
yield
to Fig.
spin-forbidden
Qp)
or molecules)
that
have
been
3, the quantum
excited
can be expressed
kz
state
by the
(3)
p Tl
(photons
equation
rl isc
of species
of population
of the emitting
excited
by light absorption
kiscl(kisc+ k, + kit)
(4)
= l/(k,
+ k&
(5)
10451
Supratnolecular photochemistry
When
when
the
intramolecular
the lifetime
excited
molecule
another
solute,
may
occur
chance
to
the
involved
states
and
the
in
that
satisfy
too
fast,
i.e.
long,
the
a molecule
of
place
arguments
states
excited
called
show
other
condition
interaction
is
-9 s may
-10
with
excited
specific
taking
than
this
spin-forbidden
some
kinetic
encounters
the
molecules.
lowest
for
organic
state
for
only
have a good
solute
are
that
spin-
molecules,
coordination
10
k
encounter
complex
T,+ B +$
pA!B]+&
representation
most
transfer7-l
chemical
important
and
either
transfer
reaction
A + B catal. deact.
of bimolecular
an encounter
processes
between
that may
an excited
state
species.8
bimolecular
electron
the
A +*B energy
+ D chemical
I k,
Fig. 4. Schematic
involve
A or products
may
a case,
longer
spin-forbidden
lowest
compounds.
live
not
to encounter
process
Simple
are
(eq. 2) is sufficiently
a chance
and
that
steps
state
2). In such
4)
states
be
excited
and
have
process.7-10
excited
allowed
may
(Fig.
those
The
of the excited
B (Fig.
bimolecular
deactivation
transfer;7-1
oxidation
or
are
energy
latter
process
processes
*12-1
the
the
reduction
energy
transfer
of
the
excited
state:
k
en
>A + *B
*A+B-
(6)
k OX
*A+B-
>A+ + B-
oxidative
electron
transfer
(7)
>A- + B+
reductive
electron
transfer
(8)
k red
*A+B-
10452
V. BALZANI
The
thermodynamic
energy
transfer
energy,
Eoeo.
processes
For
thermodynamic
the
electron
because
potentials
reductant
ground
state.
potentials
of
potential
the
corresponding
transfer
processes,
the
energy
It should be
an
content,
the redox
may be calculated
to the zero-zero
and
excited
To a first approximation,
couples
relevant
and a stronger
state
the
excitation
from the
one-electron
energy:
E(A+/*A) = E(A+/A) - E-
E(*A/A-)
Kinetic
coefficient)
(9)
= E(A/A-) + E-
parameters
(10)
(i.e., intrinsic
barrier
transfer
processes.lv12
Figure
molecular
quantities
characterize
that
place,
energy
of
supramolecular
A-B + hv-->
course,
species,l
*A-B
in
spectroscopy
state couples
ground
to intervene
to its zero-zero
of its higher
state
of the *A/A+
that,
corresponding
of an excited
is related
parameters
(eq. 8) potentials
emphasized
ability
transfer
also
and electronic
transmission
role in energy
and electron
shows
schematically
an excited
state
some
from
the
transfer processes.
and electron
between
transfer
molecular
processes
can
components
of
e.g:
photoexcitation
(11)
(12)
*A.-B -->
AL-*B
energy
*A-B->
A+-B-
electron
transfer
transfer
(13)
Supramolecular
10453
photochemistry
SAA
A-
E (A/K)
E (A+/A)
Fig.
In
5. Schematic
relevant
to
electron
transfer
supramolecular
components,
to
(Section
the
of
molecular
quantities
photoinduced
energy
and
processes.
constituted
energy
or
by
or electron
charge
several
molecular
transfer
steps
may
over
long
distances
separation
lead
7-2).
interesting
excitation
of
electron
transfer
intercomponent
that
can
supramolecular
species
process,
leads
which
state
take
is
the
place
so
to the direct
(Fig.
upon
called
formation
electron
transfer
electron
transfer
A-B
optical
of an
(14)
electron
(eq.
light
6):
A+-B-
photoinduced
->
event
charge-transfer
A-B + hv->
A+-B-
discussion
species
migration
Another
Both
the
successive
energy
indicating
diagram
14)
transfer
may
(eq.
be
11 plus
followed
eq.
by
13) and
optical
thermal
back
process:
(15)
V. BALZANI
10454
nuclear configuration
Fig. 6. Optical
electron
The relationships
transfer
Fig. 6.
processes
(l),
transfer
processes
between
optical,
Cage-type
species.
are schematized
and electron
discussed
transfer
supramolecular
in
processes
in a number
metal
Cage-type
of
systems
complexes
(4)
species
been
back
articles. v5g6*15-20
4.
4.1
have
thermal
photoinduced,
of energy
species
and
in supramolecular
in a supramolecular
Several examples
in supramolecular
(2+3),
photoinduced
by a cage-type
species.1*2v4
ligand
may
often
In this review
ligand or
be considered
as
Supramolecular
three
paradigmatic
presence
of
cage-type
photophysical
4-1-I
ligands
complexes.
are kinetically
because
of
metal
modifies
complexes
the
where
photochemical
orbitals.21
metal
of
decomposition
presence
the
and
is
well-known
that
the
of
electrons
in
the
Co(II1)
are very
o*M (e,)
of the complex.
by the following
Co111(NH3)6
It
the
antibonding
ion
of
properties.
Cobalt
complexes
labile
examples
10455
photochemistry
Such a reduction
3++e
aq
- ->
Co1(NH3)6 2+
(16)
H30+
Co11(NH3)6
2+ ->
Coaq2+ + 6NH4+
(IPCT) photoexcitation
(17)
(0 = 0.2),23
hv
Co111(NH3)6 3+
.I
<y-+
C011(NH3)6
2+ .I
(18)
H30+
C011(NH3)6
2+
or (iii) intramolecular
photoexcitation
. I ->
ligand-to-metal
charge-transfer
(19)
(LMCT)
(Q = 0.16)23
hv
c0111(NH3)6
3+ +
Co(NH3),(NH3
CoH(NH3)$NH3
+ 3+
)
H30+
+ 3+ -->
Coaq2+ + 5NH4+ + products
)
(20)
(2 1)
10456
V. Bm
Simple
chelation
because
does
Co(en)33+
reduction
loses
excitation
undergoes
In
of
1977
(en
its
encapsulated
with
redox
coworkers24
ion
so
with
NH3
octaazabicyclo-[6,6,6]-icosane)-cobalt(II1)
sepulchrate,
type
and
Co(sep)3+.
complexes
studied
of
Since
a variety
by Sargesons
a great
of metal
Fig. 7. Synthesis
quite
the
and
interesting
most
of
Co(sep)3+
the
in
cannot
reduced
From
species.
radiolysis
be observed
Co(se~)~+
+ eaq-
->
Co(sep)2+
-/I->
Co,q+
was
reaction
(Fig.
called
number
ions
7). The
have
cobalt(II1)
of similar
been
cage-
synthesized
cage-type
consequence
pulse
a capping
analogous
properties.
important
inertness
coaq2+
the
Q=O. 13 .23
group.25-28
NH,,CH,O
Co(sep)3+
LMCT
(1,3.6,8,10,13,16,19ion,
then,
radiolysis
upon
and CH20
obtained,
situation
pulse
and
performed
with
the
after
k > 25 s-1,22
its C3 axis
metal
change
decomposition
and
along
substantially
= ethylenediamine)
ligands
Sargeson
Co(en)3 3+
not
complexes
the
photochemical
point
of
encapsulation
is
Upon
of
view,
kinetic
reduction
of
in
formation
of
in strong
fact,
acid solution):29
Co(sep)2+
+ products
the
several
one-electron
experiments,
(except
exhibit
(22)
k < 1O-6s-1
(23)
10457
Supramolecular photochemistry
Such
a kinetic
intramolecular
inertness
LMCT
prevents
photodecomposition
excitation
(@ < 10W6) on
excitation:30
hv
CoIr1(sep)3+
Co11(sep+)3 +
Co11(sep+)3+
-//->
Coaq2+
(24)
+ products
(25)
hv
Co111(sep)3+.
. I -//->
Co11(sep)2+
In
spite
of
Co(NH&j
3+
their
(or
absorption
spectra.
caged
und
uncaged
basis
of
Co11(sep)2+
I- e
the
Co
different
Co(en)3 3 )
These
and
complexes
energy
(27)
photochemical
Co(sep)3
differences
hexamine
(26)
2+ + products
completely
potential
LMCT
aq
.I
curves
and
can
have
behavior,
quite
similar
similarities
be
shown
between
explained
in
on
Fig.
MC(T,)\
MC( 3T, ,
h3
nuclear
Fig. 8. Schematic
Co(sep)3+.31
potential
coordinates
energy
curves
for
Co(NH,),s+
and
8.3
the
10458
V. BALZANI
Encapsulation
does
symmetry
the
of
ligand
energy
the
first
atoms
curves
spectroscopic
strong
the
caged
region
are
nearly
dissociation
along
competition
with
Encapsulation,
pattern
the
of
ground
state.3
no
the
longer
other
of
cage
hydrogen.
8).
to
large
of the
positions
by
the
complex
potential
energy
(Fig.
8). so that
ligand
radiationless
decay
have
to
the
properties.g~10*14~40
well
known
as (i) a photoluminescent
electron
chemiluminescent
and
the
as relays
and
electron
as
anions
processes,
ten
years
attention
combination
The
Ru(bpy),z+
and
species,
(ii)
and
of
these
is extensively
used
state
an excited
of light
several
ground
prototype
an excited
(iii)
Ru(II)-
of
of
electrochemiluminescent
in the interconversion
be used
of
last
the
a unique
compound,
transfer
can
products,
30,38,39
attracted
state
the
of
reduction
water32-37
In
excited
a mediator
(Fig.
sepulchrate
photooxidation
because
(iv)
in
IPCT)
curve
from
groups
in
(or
complexes
complexes.
complexes
and
the
one-electron
research
energy
curve
state
fixed
of their
for
of
Ruthenium
complexes,
for
MLCT
hydrogen
evolution
polypyridine
the
to the dissociation
with
Co(III)
photosensitizers
4.1.2
for
to
constraints
almost
steep
the
is due
energy
ground
compete
inertness
photogeneration
simultaneous
in
in
and
transfer
kept
Therefore,
of
excitation
nuclear
particulary
by an upward
of the
Co(sep)3+
for
bonds.
branch
can
Because
are
the
potential
accounts
potential
to
by
photodecomposition
(or IPCT)
decay
the
complexes
The
IPCT)
and
constituted
Thus,
which
spectra.
(or
and
ion.
same,
introduces
which
is replaced
detachment
LMCT
motions
covalent
the
composition
is
uncaged
on LMCT
however,
units,
and
the
which
metal
absorption
radiationless
dissociative
curve
the
nuclear
coordinated
the
sphere
the
for
in
modify
coordination
CO(NH~)~ 3+
of
amplitude
substantially
surrounding
similarity
reaction
not
reactant
state
reactions,
and
chemical
in
product
and
energy.
Supramolecular photochemistry
10459
(CT)Ru(bpy);
+1.26V
Ru(bpy);
Ru(bpy$
of Ru(bpy)32+.41
relevant
are
scheme
of
data
Fig.
concerning
9.
ideal
photosensitizers
main
drawbacks
radiationless
(with,
the
the
proceeds
via
of
undergo
that
level
between
containing
reformation
p4
solutions
containing
the
ligand
radiationless
to a distorted
3MC
monodentate
bpy
either
of
loss
of Ru(bpy)32+.
decay
with
of a ligand
dependent
water
at
Cl- ions).
room
It is
reaction
transition
from
the
with
the
ground
state
an
intermediate
to
formation
or
and
level,
ligand.44v45
bpy,
lifetime
photosubstitution
activated
bond
state
strongly
_ 10-S in
the
ground
occurrence
is
that
fast
state
(from
radiationless
Ru-N
(b) the
for
relatively
the
excited
efficiency
in CH,Cl,
a thermally
3CT
competition
whose
to
the
needed
the
state
in
shows
(a)
short
and
conditions
agreed
luminescen;
cleavage
reaction
requirements
are
excited
efficiency),
to -10-I
generally
3CT
summarized
luminophores43
a relatively
experimental
temperature
and
the
Ru(bpy)32+
of
luminescence
photosubstitution
complex
with
p42
of
decay
this
Comparison
as a consequence,
a small
can
Ru(bpy)r
Some
on
-1.28V
===
chelate
of
Such
ring
an
subsequent
and
intermediate
closure
with
10460
V. BALZANI
Ligand photodissociation
linked
together
suitable
to
cage-type
make
structure,
processes
with consequent
does
not
geometry
a cage
ligand
molecular
lifetime.
can be prevented
can
thereby
the metal
and/or suitable
the
confer
slowing
down
around
also
increase
more
rigidity
to attain
that
an appropriate
decay
intensity
the cage-type
to the
the radiationless
of both emission
however,
ion.
and
ligand
coordination
3MC level would drop below the 3CT level and most of the valuable
properties
of the complex
would disappear.
Molecular
see later,
such a ligand
symmetry-demanding
the octahedral
confirmed
complex
ligand47
coordination
required
(a)
for
the
larger,
not
cryptate.
10a is clearly
The
more
suitable
Cage-type
ligand
suitable
from a
cage-type
for Ru2 +
(cl
(b)
synthesis
1. As we
cryptand
(a)
Fig.10.
is appropriate
models show
for
RuZ+
coordination;47 (b)
of the cage
complex.48
10461
Supramolecularphotochemistry
coordination
allow
the
because
bpy
coordination
been
ligands
via
of Ru(bpy)J2+
room
The
a template
Ru(bpy)j2+
(about
49 This
capable
because
not
ions,
luminescent
efficiency
to those of
state lifetime
towards
high
at
an extremely
ligand
turnover
number
Eu3+
supramolecular
luminescence
point
lanthanide
lowest excited
similar
and
a strong
a fundamental
particulary
stability
Molecular
of exhibiting
of their potential
has
is used as a photosensitizer.
complexes.
only from
very
a quite
octahedral
from a derivative
and, as expected,
assures
and
of this ligand
a longer excited
times)
104
Lanthanide
interesting
ideal
starting
spectra
vs 0.8 us)
species
almost
reaction
complex,
(1.7
photosubstitution.
4.1.3
an
Ru(I1) complex
and emission
temperature
greater
create
absorption
the parent
to
environment.
prepared48
exhibits
its larger
are
of view,
but also
of applications.
and Tb3+,
possess
quite
Some
strongly
(Fig. ll),
the
Unfortunately,
The strongest
absorption
these ions
band of Euaq3+
EJA17Fo)+heat
EG(Fo)&
.-
*Euaq
3+rqJ /
\
E~;(7Fo)+ hd
~0.02111
H,O
0.8h-i b0
t =O.llms in Hz0
3.2ms in D#
Fig.11.
Excitation
and deactivation
are
of Euaq3+.50
10462
V. B~UZAN~
occurs
absorption
excellent
emitting
absorption
coordinating
but
ability.
cage
to overcome
ions
cage-type
light
do not
ligands,
molar
to find
the lack of
the cage-type
can
(solvent)
radiationless
decay
Following
these
synthesized
displays
coupling
with
excellent
spin-forbidden
5D,,f-f
state,
effect);
(iii)
the
rate
which mainly
co-workers52
properties.
have
ligand 1, which
The
energy
level
in the
to the
of energy transfer
from the 3LC level of the bpy ligand to the 5D u metal level
sufficiently
molecular
of
O-H vibrations.5 1
of the bpy.bpy.bpy
luminescent
and
by the
decreasing
excited
Lehn
luminescent
important
guidelines,
thereby
of the luminescent
via
strong
molecules,
takes place
exhibit
be assured
water
is, of
absorption
to the luminescent
ligands
three
be transferred
lowest
with
lanthanide
By using
effect;
chromophoric
indeed
ions
i.e.
states,
of the lanthanide
with
of these
their excited
a possibility,
of the
nm
bands.
Complexation
course,
393
properties
ways to populate
at
is
is an efficient
of UV light absorbed
by the
very
(-10m5M)
dilute
convert
about
photonss4,
particular
aqueous
solution
1% of the incident
a quite interesting
this complex
UV photons
result
into emitted
for several
materials.
is able to
visible
applications,
in
Supramolecular photochemistry
Ligand
10463
Metal
30'3
e
p
20-
5
l&llo-
Fig.12.
Considerable
effort
luminescence
caging
be
not
into
imply
levels
at
the
(b)
or
by
be efficient;
a close
light
this
the
presence
of
of
ligand-centered
higher,
contact)
of
otherwise,
the
luminescence
efficiency
absorption
to
some
between
or
level;
the
the
energy
the
degree
the metal
and
metal
should
that
of
the
channels
level
be
for
would
be
compromised;
excited
centered
of interaction
to
charge-transfer
new
ligand-centered
other
have
ligand
than
would
the
by using
(a)
from
implies
complexes
improve
requirements
luminescence
transfer
energy
further
additional
slightly
decay
the
to
two
metal-centered
and
populated
that,
occurrence
lower,
devoted
In doing
radiationless
available
currently
consideration:
luminescence
fast
is
properties
ligands.55
taken
states
levels
(and,
the coordinated
should
therefore,
atoms
of the
the
Eu3 +
ligands.
Excellent
luminescent
complexes
of
Promising
results
2,56
properties
and
have
by the Tb3+
also
been
are
by
complexes
obtained
incorporate
exhibited
of
by using
N-oxide
256
and 3.5 7
cryptate
ligands
groups.
10464
V. BU
cp
Ph
4-2
several
cages
that
different
It
can
be
well
know
due
cryptand
strand
this
photocleavable
the cryptand
to create
result,
a high
would
Lehn,
light-controlled
of the
ether
jumps
2.2.2
cation
have
polyoxadiazaLehn
alkali
the
one
decrease,
solution.
introduced
of
these
compounds
or pulses
of cation
the
ion
of one
affinity
into
and
metal
Photocleavage
recently
into
Two
reported.
by
towards
bond
In principle,
been
ago
size.
to have
excitation.
a substantial
metal
et al. 62
and
long
cavity
cause
light
recently
2.2.1,
selectivity
different
release
13).
2.1.1,
be necessary
by
have
prepared
2-nitrobenzyl
(Fig.
closed
problem
the
to the
a consequent
obtain
that
exhibit
complexation
with
to this
cages
it would
and/or
criptands,
coworkers,61
the
opened
approaches
is
photo-flexible
of applications,
types
macrobicyclic
of
and
Photo-cleavable
For
bridges
could
To
the
of
be used
concentrations,
Supramolecularphotochemistry
that would
cleavable
be quite
chelating
described.6
useful
ligands
investigations.
for physiological
for alkaline-earth
cations
R-&O:
Control
of the cavity
by taking advantage
reversible
photoisomerization
azobenzene
capped
cryptands.62
size without
obtained
crown
disruption
tram->cis
takes place,
reaction.
ether
For
metal cations
8, whose
the pyridine
nitrogens
can coordinate
are directed
in this cis
the ability
caused by a
example,
the
small metal
cavity
preferably
in the tram
towards
unit
binds large
bridge
is
conformation
the crown
plane
and
conformation
to extract
trans-
of the azobenzene
bridge,
larger
by the 2,2-azopyridine
changes
7 binds preferentially
photoisomerization
yielding
of the structural
co2+,
m-n-1
Fig.13. Photocleavable
replaced
Photo-
R=H:m-n=O
m-1. n-0
m-n-l
known
10465
heavy
of the bridge.
As a
Ni2+,
photocontrolled.
containing
two
described.66
photoresponsive
isomerizable
In
towards
various
towards
the rate
of hydrolysis
photocontrolled.
azo-benzene
azobenzene-capped
ability
cylindrical
substrates
units
the
ether
also
been
has
cyclodextrin,
and
crown
the
catalytic
of p-nitrophenylacetate
bridging
activity
can
be
V. BALZANI
7
Vogtle
and
macrocyclic
species
light excitation,
have
co-workerse8
synthesized
9 which contains
the very
three azobenzene
with a consequent
interesting
units. Upon
isomerization
on structural
changes
in photoflexible
systems,
see
chapter 7 of ref. 1.
H
9
4.3.
Photochemistry
currently
fullerenes.70
of
incarcerated
of spherical-type
attracting
much
molecules
molecules
attention:
with internal
carcerandseo
voids
and
10467
Supramolecular photochemistry
In carcerands
molecules,
the internal
providing
characteristics
phase.
reactions
them
and
The
are
then
these
is large
inner
which
possibility
within
cavity
new
phases
arises
perform
reactive
species
radicals
prepared
and studied
in appropriate
first,
exciting
photochemistry
Cram
and
is
the
photofragmentation
and found
that
imprisoned
or unstable
Interesting
questions
nm) required
example
species.
of
the
guest
Many highly
can
this
new
of cyclobutadiene
studied
of a-pyrone
within
irradiation,
the
likely
be
branch
of
performed
by
photoisomerization/
a carcerand-type
species
cyclobutadiene
remains
arises
is effective.
luminescent
in argon
of cyclobutadiene
Absorption
based
translocation
chemical
on
of a large-cavity
systems
fundamental
the
carried
of
to
the
light
at 8 K.
(200-250
to
by
genes,
study
which
Systems
out
crown
compound
studied.71
recognition,
(enzymes,
discovery
way
Host-Guest
molecular
processes
matrix
by the dimethoxybenzene-
is
and exists
is a possibility.
properties
5.
is
breaks down to
acetylene
cyclobutadiene
when is prepared
opened
where
inner phases.
They
On further
as it does
Life
bulk
photochemical
isomers
acetylene,
contains
peculiar
of the
as a singlet.
The
matter
other
thermally
give
of
with other
taming
co-workers.@e
to
phases
to interact
very
exhibit
regardless
is prevented
The
which
to host
maintained
molecule
like
enough
ethers
of
transformation,
extremely
antibodies,
by
complicated
etc.).
Pedersen72
molecular
and
The
in 1967
recognition,
lo468
V. BALZWI
transformation,
and
synthetically
accessible
concave-oriented
almost
exclusively
have
prepared
been
species
a great
(guests).
processes
This
and
photochemical
on
structure-specific
electron
intermolecular
and
The
is
in Section
approach
the
adducts
are
properties
photochemical
separated
5.1
characterized
by
Reviews
of
on
elsewhere.
the
ion-pairs,74-77
chromoionophores
can be found
species
the
and
compounds,84-87
Cage-type
described
capable
and
compounds
separated
species
to
give
and
are
of
those
section
host-guest
photophysical
studied;
properties
compared
in this
to
photochemical
photophysical
then
Polyammonium
hydrogen
in determing
the
(iii)
the
adduct
are
exhibited
by
the
components.
Because
adduct
and
where
Supramolecular
not
properties
inclusion
molecular
two
and
role
be discussed.
cyclodextrin
(ii)
the
as
complementarity
but
in the investigations
chosen;
of
investigated
(i)
light-induced
defined
properties.
not
molecular
4.
taken
following:
will
the
(hosts)
components
a key
complexes,78.79
of DNA,*4188
are discussed
play
forces
photophysical
fluoroionophores,su-84
of
systems,
synthetic
shapes)
previously
of convex
examples
photophysical
donor-acceptor
adducts
of
years
species
(particularly,
convex
25
to complement
molecular
host-guest
made
interactions
photochemical
begun
last
simple,
chemistry
illustrates
in
and
based
thus
the
complexation
interactions
structure-specific
systems
section
species
concave
In
of concave
selective
occur
supramolecular
has
variety
for
that
between
species.
convex-oriented
and
with
processes
molecular
chemistry73
developed,
the
translocation
macrocyclic
of their
bonds,
formation.
high
cyanide
electric
receptors
charge
complexes
Co(CN),3-
gives
are
rise
and
very
with
their
CO(CN),~-
capacity
suitable
to very
stable
to form
species
I:1
for
adducts
10469
Supramolecularphotochemistry
with
the
shown
protonated
in Fig.
the same
as that of free
partners
transfer
transitions.
constants
a
of
the
The resulting
14.8g
between
with
forms
that
peripheral
cannot
give
The relatively
contribution
nitrogen
absorption
CO(CN)~~-,~~
polyazamacrocyclic
of
to
values
for
adducts
charge-
of the association
interaction,
hydrogen
bonds
complex
anion
the
is essentially
low-energy
an ionic-type
from
atoms
spectrum
as expected
rise
high
receptors
probably
between
and
the
hydrogen
cation.
ZJ
-(CH& 4
HN
NH
I--(CH&--;
[32]ane-Ng
[32]ane-N6-Cg
[24]ane-Ng
[24Jane-N3
Fig.14.
Structures
CO(CN),~- undergoes
28)
that
can
COAX-
near
be easily
+ H,O ->
of some polyazamacrocyclics.
a very
clean photoaquation
followed
Co(CN)&H,O)*-
where
UV
region,
throughout
the
photoreaction
is high
two
from
isosbestic
.points
The
and
changes
@ = 0.30
+ CN-
photoreaction.
(@,=0.30)
spectral
reaction
quantum
independent
are
in the
(28)
maintained
yield
of
(eq.
of
the
excitation
V. BALZANI
wavelength,
primary
acidy
of the solution
photochemical
significant
concerted
is predicted
process
photodissociation.
simple
is
1.2-5.0),
and solvent.
thought
to
dissociative
rearrangement
initial
be
step
The
CN-
without
fragment
theoretically.g 1
When
the
COAX-
containing
solutions
aqueous
photoexcited,
same
photoaquation
the
reaction
adducts
are
exhibited
by
yield
of the photoreaction
free
COAX-
introduce
(Table
Co(CN),j-,
formation
reduces
to a multiple
discrete
is noticeably
1). g2 Since
adduct
(pH
excited
formation
does
for
not
One striking
the quantum
observation
(Table
1) is that adduct
equal
number
of
CN-
groups
are
permitted
to
undergo
photodissociation.
Table
1.
alone
Co (CN)
63-
1.0
0.33
1.2-5.0
0.30
([24]ane-N6H6)6+ .CO(CN)~~-
2.5
0.15
([24]ane-N8H,)7+.Co(CN)63-
2.5
0.15
([24]ane-N8H8)8+ .CO(CN)~~-
1.0
0.16
([301ane-N10H10)10+ .CO(CN)~3-
2.3
0.14
((32Iane-N6H6-C9)6+ .CO(CN)~~-
1.2
0.11
([32Jane-N8H8)8+.Co(CN)63-
2.5
0.10
10471
Supramolecular photochemistry
In
agreement
results
obtained
adducts
with
cobalt
ligands
only
2 of
are
indications
be
large
can
the
the
can
the
complex
CN-
with
rationalized
32-atom
be enclosed
involved
macrocycles,
encirclement
likely
free
of
structure
in
the
models,
following
receptors,
within
ligands
space-filling
ring
the
in hydrogen
CN-
of
bonding
to
CO(CN),~-
(Fig.
escape.
For
in Fig.
In
octahedral
so that
by the ring
is that shown
way.
the
macrocycle
the
four
15a).
leaving
the
smaller
is not possible,
15b, with
3 labile
CN- ligands.g2
(gbi p+Ny
-N++NH+
Fig.15.
Proposed
in
supramolecular
solution
macrocyclic
Besides
adduct
of
offering
formation
mixed-ligand
toward
appears
5-2
specific
also
the
charge,
receptors
by
products.
crown
properties
residual
protection
find
complexes
interesting
orienting
In
with
interaction
to
give
ability
size.92
against
photodissociation,
applications
cases,
in the case
complex
stable
of the adducts.
the
metal
which
adducts,
reactions
photochemistry
Pt(bpy)(NH,)22
on
formed
polyammonium
a square-planar
needed
adducts
the
photosubstitution
favorable
probe
ethers
of
and
of different
also
NH+
COAX-
a generic
might
Wwy)WH3)22+ is
of
between
to be a valuable
Aromatic
structures
NH+
-NH+-
exhibits
namely
ion,
and
most
electric
residual
V. BALZANI
10472
-electric
y
hydrogen bonds
~-unfilled
coordination sphere
IC- fl stacking
Fig.16.
interaction
reaction
and
a variety
is
on
this
Furthermore,
both
photophysical
absorption
are
and
Because
the
NH,
undergoes
at low
of
ligands
of these
design
clean
and
adducts
of
by
addition
and
practically
acetonitrile,
is insoluble
of
emission
18C6
identical
showing
that
Pttbpy)(NH3)22+
hydrogen
bonds.
The
(Fig.
spectra
between
to
temperature
in
Pt(bpy)(NH3)22+
photochemical
of the
there
CH2C12,
adduct
and
of
free
intense
The
structured
18C6,
which
absorption
with
nn*
band
its
a 1:l
electronic
are
kept
maxima
on the
maximum
metal-perturbed
data
indicate
triplet
that
the luminescent
ligand-centered
adduct.
(Fig.
The
18)
Pt(bpy)(NH3)22+
transitions
shows
but it can be
in CH2C12
is a negligible
and
luminescence
in
17) to give
those
307
(Fig.
16).
photochemical
high
properties,
(Fig.
interest.g4
[Pt(bpy)(NH3)2](PF6)2
dissolved
bpy
luminescence
of solvents.g3
for
complex
exhibits
suitable
interactions
Pt(bpy)(NH&*+,
ability
charge
level.
excited
When
in
interaction
together
at
319
bpy
at
by
and
ligand.
486
nm
temperature
state
is a
aromatic
Supramolecular
lo473
photochemistry
onon
3
w
18C6
DB30ClO
DB24C8
Aono?i-v-
(xJwuJ 43
0
DB36C12
0700
[
0-0
BMP32ClO
8)
e/o
0
BPP28C8
BPP34ClO
fPo~@-onoAo
(wJ@eL/o I
DN30ClO
BPP40C12
l/5-DN38ClO
DA42ClO
Fig.17.
Crown
ethers
used as hosts
for Pt(bpy)(NH3)22+.
V. BAUANI
10474
!J
;_
290
340
\
A , nm
spectra
of DB30ClO
0
Fig.18.
Absorption
Pt(bpy)(NH3)z2+
\
1
)&_
390-
.
Y.
300
400
Fig.19.
Luminescence
4r
.-
----Pm
600
700
500
A ,nm
spectra of DB30ClO (---.), and of the adducts
of Pt(bpy)(NH3),z+
Supramolecular photochemistry
macrocyclic
polyethers
adducts
are
crystal
X-ray
again
that,
betweeen
the
Figs.
17 have
18 and
strong
changes
(see,
e.g.,
of
the
against
adduct
anthracenophane
host
photocyclization
reaction
2+,
Pt(bpy)(NH,),
photo
decomp0sition
band
hJ
7
19).
with
is
the
in
0
ck
/NH3
;Pt
ON
CJ
in
causes
of
the
a new,
broad,
region
of the
+
interesting
When
CH2C12
photoreaction
shown
Pt(bpy)(NH3)22
17).g7
20).
behavior
As shown
Particularly
photoexcited
no
place.
ethers
cases
Furthermore,
(Fig.
take
quenching
in the red
place
(donor)
formation
appears
(Fig.
however,
the
In several
DA42ClO
takes
crown
and
This
interaction
can
adducts
photoreactivity.
assumes
photochemical
aromatic
spectra
single
polyether
in detai1.g3*g4*g7*g8
absorption
Fig.
nn *
(acceptor)
of DB30C10,
luminescence
is protected
case
investigated
I:1
complex.95*96
macrocyclic
the
18C6,
receptor
and
of
DB30C10,
the
metal
complex
spectrum
the
in the
short-lived
guest
the
with
luminescence
and
been
that
the
photophysical,
2+ adducts
with
bonding,
of
of the metal
spectroscopic,
Pt(bpy)(NH,),
showed
hydrogen
units
in the place
adduct
around
besides
ligand
used
the
studies
aromatic
in Fig.
For
configuration
suggests
of
17) are
formed.
diffraction
U-shaped
The
(Fig.
10475
is
the
free
solution,
In
its
adduct
is
observed.
a
with
This
12+
NH3
I
+ ADDUCT h3_
Fig.20.
Photochemical
their
adduct.
behaviour
of Pt(bpy)(NH3)22+,
DA42Cl0,
NO
photoreact ion
and
10476
V. BALUNI
h3-
hJ-
h3
Host
1
a
Fig.21.
Schematic
Solvent
of
explanation
behavior
the
of Pt(bpy)(NHg)22+,
different
DA42Cl0,
photochemical
and their
adduct
(see text).
suggests
that,
between
the
as schematized
two
aromatic
a structure
which
solvent
prevents
and
an energy
level
reactivity
of
the
accounted
for
by
luminescent
In
the
host
the
conclusion,
appropriate
towards
spectroscopic
the
supramolecular
photoreactions
and
the
of
guest
the Pt complex
the
anthracenophane
from
photoreaction
of
the
host.
host
In
quenching
of the
luminescence
guest
adduct
formation
and
on
of a charge-transfer
excited
states
assembly
of
structure
and
photophysical
is inserted
the
photocyclization
presence
reactive
21,
moieties
protects
diagram,
and/or
in Fig.
can
of the
two
can
two
protect
with
the
terms
of
and/or
can
be
below
the
components.
components
profoundly
properties.
state
in
the
into
an
components
change
their
Supmmolecular photochemistry
5.3
Lasalocid
The
absorption,
&=25000
the
nm,
centered
nature
lifetime
of
and
of
the
is
photodecomposition
ligand
in CH,CI,
22)
have
slightly
salt.
the
excited
state.
luminescence
(LC)
band
solvent
and
ionic
strongly
affected
can
be observed
Cr(bpy)33+
Me
studies
is nearly
strength,
by
Et
spectrum
have
from
the
the
medium.g
Me
A anion LAS-.
nm,
the *E
shown
independent
solution.
is
luminescence
while
in CH2C12
as a
( &a,=307
originates
of
extensively
in CH,Cl,
The Cr(bpy)33+
Detailed
band
been
absorption
properties
soluble
Its
centered
solution).
Me
Fig.22.
is only
photochemical
Fig.
hexafltiorophosphate
M-cm-
energy
complex
by an intense
(h max =728
metal
This
or
dominated
Cr(bpy)33
luminescence,
investigated.gg
perchlorate
with
(bpy=2,2-bipyridine,
3+
Cr(bpyI3
anion
lo477
that
of
the
luminescence
g
No
10478
V. BALZANI
The lasalocid
nonpolar
A anion (LAS,
solvents.
This molecule
an aromatic
ring
in
which
band (h,,,
intensity
solution.
LASH
species.
Cr(bpy)33+ and
Since
in
the
absence
Cr(bpy)33+
contrast,
of
electronic
solution
should
at the beginning
interaction
cause
addition
an increase
the absorbance
that Cr(bpy)33+
electronic
interaction
the metal
complex.
luminescence
and LAS
Confirmation
of
1:l
state lifetime
LAS - luminescence
fluorescence
quenched
was
measurements.
increase
for
intensity
from
addition
of LAS-
by a static
a strong
increase
An association
both
of
values
absorption
LAS-
also
higher
than
lifetime.
of the
mechanism.
in the LAS
for LAS
constant
and
causes
unity,
of -106
emission
a noticeable
at 728 nm;
a plateau
is
of
with an intensity
comes
intensity
obtained
The
formation
fluorescence
take place
LAS- causes
[LAS-]/[Cr(bpy)33+]
reached
for
clearly
can only
of
behavior
of LAS
and only
By
in the LC band of
adduct
The
measurements.
concentration
addition
to a
This
Further
LAS
in absorbance.
decreases
indicates
Cr(bpy)33+
of
[LAS-l/[Wbpy)3
from
in the
lo479
Supramolecular photochemistry
Looking
at
carboxylate
group
intraligand
The
This
ligand,
interaction
leads
anions
sphere
account
the
for
under
lifetime
6.
(Fig.
a linear
23b)
(ii)
the
as a consequence,
in
level
(Fig.
species
with
and
are formed
bulky
composed
groups
of
or
of
the
interaction
can
intensity
and
while
the
the
effects
increase
luminescence
related
by a ring
on either
interlocked
a
Fig.23.
the
solvent
rigidity
for
ligand,
intensity)
species
which
is threaded
end.
Catenanes
rings.
Catenanes,
b
Schematic
knots.
in
of Cr(bpy)33+.100
catenanes,
23a)
account
electronic
with
absorption
fluorescence,
can
fragment
are
in
(iii)
centered
a bpy
electronic
to
complex.
and
interaction
The
the
an
LAS-
and parallel
(i)
increasing
ion.
LAS-
and
from
the
by replacing
close
are
that
Cr3+ ion in an
around
of
(iii)
metal
the
Rotaxanes,
Rotaxanes
and
variation
of
points
(and,
of the 2E metal
by
observed
quenching
described
the
PFg-),
of the
of LAS-
moiety
ion
see
(presumably
association
phenyl
can
the
approach
ring
this
of the Cr3+
(e.g.,
one
of LAS- wrapped
of
the
screening
static
can
the phenyl
results
coordination
the
LAS-
the tail
between
some
other
of
with
expected
(ii)
models
molecular
PF6- anion).
a bpy
CPK
representation
of
rotaxanes,
C
catenanes .
and
10480
V. BALZANI
rotaxanes
and
related
supramolecular
viewpoint.
architectureslo
much attention,
analytical
fairly
knots,
(like
very attractive
received
and
species
high
helicates,
methods
yields.
etc.
photophysical
made
Nowadays
have
been prepared,
investigations
23~)
achievements
their
catenanes,
in synthetic
synthesis
with
rotaxanes,
knots,
have
been
are
from an aesthetical
systems
possible
several
Fig.
performed
so far
and
on such
species.
6.1
Catenands
A clever
synthesis
and
metal
route
around
tetrahedral-type
catenates
to obtain
a
interlocked
metal
complex.
Taking
coordination
geometry
imposed
catenates
and 13,
where
and
16,
Starting
from
coworkers102
to the corresponding
the coordinating
cases of Cu2(3-cat)2+
species
is the template
advantage
of
have
prepared
14.
free
contains
the free
a catenate
catenands
the
metal
of these
(catenands)
are disentangled.
which
(dap)
Demetalation
ligands
subunits
yields
11
In the
the Cu(3-cat)+
and a catenand
a number
the
unit 10,
catenates
species
of catenates
moieties.
of other
luminescence
catenates
have
been
moieties,
as expected,
properties
of
investigated
(Table
behave essentially
the
dup.lo5
showing
independent
properties
dap units,
around a proton
Zn(2-cat)2+
that
of
the
but involves
species
exhibit
catenands
2).103*104
as the dup
The
and
catenand
chromophoric
catenands
catenand
in a catenate-type
several
differ
protonation
does
coordination
structure.lo4
ligand-centered
from
not
those
of
concern
(LC) fluorescence
and
and
10481
=-CH,+CEC
16
j*CH2-
b=-CH2Cti2fOCH2CH2j,
M -CuU) M'-Com)
15
phosphorescence,
divalent
ion.
luminescent,
considerably
The
more
Co(2-cat)2+ and
as expected
because
which occurs
and
spectral
region,
charge transfer
16, as expected,
the
luminescence
in the case
of the
Ni(2-cat)2+
complexes
are not
of
displays
catenand
of
radiationless
decay
excited
to the lowest-energy
triplet
species
two luminescence
and
the
a fast
metal-to-ligand
from
perturbed
catenate
catenand
bands,
moieties,
moiety,
which originate
respectively.
however,
is
The
strongly
10482
V. BALZANI
quenched
by the adjacent
emission
can
G-catenate
be observed
at room
unit.lo3
For Ag(2-cat)+
temperature,
whereas
no
in rigid
species
15
does
the
Cu-containing
derivatives
one.
display
behavior.
In particular,
not
moiety
In
luminescence.
quenches
conclusion,
varied
their
exhibit
and
the luminescence
11,
13,
interesting
luminescence
This
and
their
photophysical
can be tuned
over
the
Luminescence
properties
(nmlb
max
(ns)e
@d
dap
396
2.2
0.29
2-cat
400
2.0
0.42
H(2-cat)+
555
11.0
0.022
Li(Z-cat)+
400
2.5
0.35
Cu(2-cat)+
730
175
0.0011
Ag(2-cat)+
Zn(2-cat)2+
463
2.0
0.082
3-cat
400
2.4
0.33
Cu(3-cat)+
Cu2(3-cat)2+
400;725
730
2.4;181
177
0.0007
Co(2-cat)2+
Ni(2-cat)2+
0.054;0.0011
CuCo(3-cat)3+
aCH,Cl,
bMaximum
quantum
band
excited state
yield
at room temperature;
10483
Supramolecularphotochemistry
6.2
Rotaxanes
and
catenanes
featuring
charge-transfer
interaction
Electron
highly
donor-acceptor
efficient
catenate
18
groups
involved
template-directed
performed
by
hydroquinol
bipyridinium
(paraquat,
macrocycle
provides
synthesis
Stoddart
in the electron
electron-rich
tetracatianic
interaction
and
of
and
PQ2+)
units.
17 and
19 is threaded by a hydroquinol
Si-derivatives
the tetracationic
macrocycle
19 is interlocked
two hydroxiquinol
(21).
PO-
Ol
0
0
cep,
OSIPI$
17
the
unit that
18
18
r 0-
are the
In the catenane
units.
17
The
electron-deficient
In the rotaxane
with bulky
Pr!#0
rotaxane
interaction
the
is then stopped
20 which contains
for the
coworkers.106-108
donor-acceptor
units
the basis
21
V. BALZWI
The
have
electrochemical
been
obtained
investigated.
on
(DMB)
in
electron
which
between
displaced
splitting
paraquat
units
paraquat
oxidation
of
paraquat
more
(i)
the
that
is
unit,
unit,
the
first
which
reduction
tetracationic
oxidation
some
Both
electronic
such
in 18,
is indeed
the
waves
waves
and their
an expected
electron-acceptor
more
difficult
be
interacts
with
oxidized,
interacts
with
correlations
can
be observed
17, 18,
and
their
of
electrochemistry
monoelectron
the
negative
and
two
only
the
paraquat
of
paraquat
reduction
two
characterized
processes.
For
units
reduced
paraquat
potential
is
than
are
paraquat
between
the
simultaneous
reduction
of
units
Reduction
17
is
similar
of
the
to that
the
since
repulsion
both
in the
components
electrostatic
rotaxane
the
is
units
which
to
positive
unit is involved
of
with
hydroquinol
their
1,4_dimethoxybenzene
potentials
interaction
and
a more
units.
This
the results
to
The
one
inside
unit,
is
Similar
potential.
at
there
positive
the
17 and 18
18,
20 two distinct
than in 20.
makes
unit,
17,
units
hydroquinol
hydroquinol
19,
the
alongside
oxidized
place
the
is much larger
because
oxidize,
17 takes
indicates
towards
behavior
of
reduction
of
to
of
24 and 25 compare
observed,
properties
donation
interaction
are
to
as expected
macrocycle
are
and
Oxidation
compared
spectroscopic
lo8 Figs.
oxidation
components.
potential
and
by
two
25).
cyclophane
simultaneously
at
units.
more
macrocyclic
bis-paraquat
at
decreases
charged
The
consecutive
bis-paraquat
follows
bis-paraquat
of the
(Fig.
reduction
two
electrochemical
less
the
Second
negative
ring
cyclophane
of
19,
Supramolecular photochemistry
+2.0
I
Fig.24.
+ 1.0
I
Oxidation
of
10485
rotaxane
17,
catenane
18,
their
and
components.108
except
the
reduction
of
the
interaction
because
hydroquinol
does
not
the
spontaneously
alongside
interaction
unit.
unit
positional
units
creates
second
reduction,
paraquat
units
first
indicating
and
18
spectroscopy.
is
also
108
for
occurs
that
electron
obtained
The
model
with
species,
stoppers,
bead
18
the
two
otherwise
gradient
(Fig.
25).
charge-transfer
donor-acceptor
absorption
the
of the paraquat
from
which
in donor-acceptor
the
the
In the catenane
between
an electrochemica1
potentials
units
involved
compared
difference
however,
evidence
paraquat
reduction.
is less
the
negative
triisopropylsilyloxy
after
paraquat
more
in a rotaxane
Such
identical
bulky
at
of
unit. Interestingly,
have
unthreads
the
occurs
that
spectra
of
for both
interaction
is
units.
interaction
absorption
The
and
17
in 17
emission
and 18
are
V. BALZANI
-1.0
I
21
19
i;
I
17
\
\2
Fig.25
Reduction
of
17, catenane
rotaxane
18,
and
their
components.*u*
noticeably
different
components.
visible
In
region
transfer
from
the
sum
a broad,
both
17 and 18 that
transition
from
the
paraquat
bands
coincide
nm),
nature
of
molar
absorption
that
units
of 20
consistent
(A=478
interacting
of 17,
with
fluorescence
quenched
in both
Investigations
rotaxane
and
can
suggesting
that
a
the
present
be assigned
because
of
in 18
nm)
both
residue.
results
hydroquinol
units
is
the
is
these
identical
the
practically
hydroquinol-type
This
which
of
to
Furthermore
of 18
the
the
units
maxima
cases.
in
to a charge
The
two
luminescence
the
is
respective
hydroquinol
A=478
paraquat
of the
band
expected
in
(at
the
of
units
with
weak
residues.
as
coefficient
interact
spectra
z-electron-rich
the n:-electron-deficient
twice
the
particular
for
the
of
conclusion
show
almost
that
is
the
completely
17 and 18.
are
catenane
presently
structures.
extended
The
to
more
supramolecular
complex
system
10487
4 PF;
Pr3Si
xx
O&
0
-o-
o-o,0
+N*+
4+
=
=
=
=-
-=
+N
Fig.26.
in Fig.
shown
A molecular
26 consists
units
and
experiments
have
demonstrated
forth
between
species
at
temperature.
a bis(paraquat)
that
which
groups
interactions
between
due
to
the x-electron
donor
much
smaller
than
rate
hydroquinol
units
luminescence
of the hydroquinol
The
shuttle
construction
of
of
decay
shown
in Fig.
molecular
26
the
transfer
residues
stations
process
the
the
is 13.2 kcal
the shuttle
of
in
in
frequency
photoexcited
is quenched.1 to
is a first
machines.to8.*09
by an external
varying
paraquat
(z = 1 ns). As a consequence,
residues
back and
charge
the
NMR
hydroquinol
Dynamic
by
favorable
acceptor
two
of the supramolecular
positions
the
containing
shuttles
hydroquinol
is
bead
controlled
the thread
mol-I,
the
be
chain
bead.109
stations
can
N+
shuttle.l@J
of a polyether
hydroquinol
step
towards
If the position
the
of the
V. BAIZANI
be used as a molecular
memory
to reach
such a result,
in a molecular
computer.
In order
where
the
bead prefers to stay in one of the two stations. This can be done by
using
two different
electron
donors:
the
into
chemical
maintains
electron
transfer
ordered
arrays
to
artificial
sites
electron
controlled
arrays
and
in Section
molecular
manner.
is
fuels)
that
energy
and
fossil
light
chemical
is absorbed
excitation
centers)
The reducing
where
reactions
species
to be used
by
energy
a
and oxidizing
is
charge
species
which lead to
2, supramolecular
components
for
research
building
is
up
transfer
species
can also be
via covalent
bonds (Fig.
to synthesize
of molecular
energy
sunlight
systems.
plants,
(reaction
An important
by linking
firewood,
of supramolecular
As mentioned
obtained
In green
takes place.
photosynthetic
where
process
(food,
components
is based on photoinduced
of pigments,
reaction
the design
energy
processes.
specific
molecular
natural
converted
or (more difficult)
abacus.
Covalently-linked
Photosynthesis,
preferentially
oxidation of X. Electric
7.
so obtained
will
separation
bead
photochemical
channeled
the
linear
components
processes
can
where
take
photoinduced
place
in
Supramolecularphotochemistry
7.1
Photoinduced
component
In
the
model
last
investigations
electron
the
electron
few
years
many
explored
and energy
transfer
the
processes,
A detailed
discussion
of electron
and energy
transfer
(Section
two-
theoretical
photoinduced
two
emphasis
on
components
of the theoretical
processes
can be found
in
processes
in
3).
and
made
of
with particular
between
supramolecular
in
and
mechanism
interaction
Photoinduced
transfer
experimental
electronic
aspects
of
energy
systems.
have
problem
and
10489
energy
of two
transfer
covalently-linked
molecular
a
01
0b
,electron
*A-L-B
back
electron
transfer
A-L-B
A-L-B
components
can
photoinduced
electron
transfer
process,
be
(A and B) linked
schematized
transfer
and energy
in a supramolecular
as
is followed
transfer
in
Fig.
system
by a connector
27.
In
(L).
general,.
is followed
by the radiative
104!lO
V. BUAM
and radiationless
deactivation
From an experimental
cause
the quenching
(A).
Formation
by
spectroscopy
viewpoint,
the
experiments.
be demonstrated
experiments.
transient
recording
its
and A-L-*B
The presence
mentioned
experimental
species)
transfer
of the absorbing
species
B-
absorption
information
A+-L-B-,
and energy
A+-L-
species
can
spectrum
in
of the A-L-*B
by flash spectroscopy
Kinetic
both electron
of the luminescence
of
demonstrated
of the excited
electron
systems
based
examples
as well as by luminescence
(i.e.,
the lifetime
of the *A-L-B,
will be discussed
coworkers11
by the above
processes
molecular
transfer.
electron
donor
schematic
Verhoeven,
transfer
length
group
and
processes
and
Fig.
is possible.
27a),
A-B distances
the
methoxynaphthalene-spacer
of the connector
A-L-B
A-L
species
model.
an
in systems
electron
spacers
systems
various
and rigid,
and
investigated
span
A and of 4 to 12
transfer step (Fig.
by comparing
that
of
a linear
decrease
of
of the A
solvents
with
acceptor
freedom
of -7-15
For
on the
unit (A in the
are saturated
and
norbornylogous
The
Hush
of
reviews
investigations
chromophoric
range of centre-to-centre
fluorescence
A few other
Paddon-Row.
B components
interposed
of
(B),
as connectors
the attachments
species.
out systematic
dimethoxynaphthalene
representation
dicyanovinyl
in supramolecular
of photo-
photoinduced
transfer
on covalently-linked
Electron
7.1.1
can
techniques.
and energy
of these processes,
flash
species
be
the
suitable
arrangement
exponentially
with
Supramolecular photochemistry
10491
CN
CN
two-component
Fig.28. Dimethoxynaphthalene-dicyanovinyl
systems
increasing
length
1.2~10*~,
and
detailed
for
and
dipole
free
distance.
by
using
very
values
agreement
conductivity
signal
the
charge-separation
of
28)
systems
shows
that
two
of
by
the
the
the
energy,
the
of
with
the
been
state
therefore
electron
used
are
to
obtain
rate
rates
lie
much
slower
in
through
D) are
decay
of
in
the
27a)
the
the
the
of
for
the
reaction.
Marcus
than
bent
l2 The
constants
the
of
been
disappearance
Fig.
between
stereochemistry
transfer
the
the
have
(26-77
The
transfer,
Comparison
the
values.
to monitor
electron
reactions.
in
expected
and
(back
moments
on
compounds
conductivity.*
the dipole
energy
depend
microwave
for
that,
that
free
reorganizational
series
parameters
namely
same
fact
time-resolved
has
differing
separation.
states
charge-recombination
and
12-bond
3.3x10*,
charge-separated
charge-recombination
region12
example,
A+-L-B-
charge-separated
Such
On
obtained
substantial
and
energy,
sphere
for
is complicated
activation
of the
measured
constants
outer
being,
reaction,
and
moment
high
s-l
separation
the
solvent
connector,
of these
the
change
the
1.3~10~
charge
determine
both
of
analysis
14
inverted
activationless
rate
constants
connectors
bridges
is
(Fig.
slower
lo492
V. BAUANI
with respect
transfer
with
to the stretched
theoretical
predictions
that
coupling
an all-trans
arrangement
of (T
cases,
Section
charge transfer
3,
observed.117g118
Fig.
6)
and
Such processes,
coefficient
the radiative
yield
and
acceptor
electronic
Energy
7.1.2
electron
features
radiationless
developed
be used
(exchange)
band
in
and
by quantum
to calculate
the
donor-
species
This
where
both
between
two-component
is
transfer
even
more
processes
two
have
may
electronic
supramolecular
certain
apparent
in
be viewed
as
states.1
Recent
has
further
species
this concept.
connectors.
benzophenone
Following
chromophore,
benzophenone
is populated
with formation
of its lowest
and L
of the
the
and
lowest
energy
triplet,
energy
transfer
which
is
processes
about
twice
fall-off
that
triplet
transfer
takes place,
is exponential,
obtained
for
transfer.
a series
B is naphthalene,
analogous
been
(obtained
energy
19
transitions
on
also
absorption
common.1
supramolecular
work
and
in
can
electron
coupling.
transfer.
transfei
transfer
of the emission
data)
have
are important
of the charge
rate constant
lifetimes
emission
(optical
absorption
to
state
of
naphthalene,
according
to the
processes,
this
The rate of the
with a coefficient
electron
transfer
in
can be explained
on
Supramolecularphotochemistry
Singlet-singlet
and
energy
transfer
co-workers124,125
previously
discussed
carbonyl
group
systems
the
replacing
of
twice
exponential
indicates
7.2.
systems
transfer
identical
(Fig.
dicyanovinyl
extent
28),
to
the value
on the number
for electron
of
again an exchange
the
rate
these
component
of C-C
fall-off
transfer
dependence
for
In
of the exponential
obtained
those
except
fragment.
depending
The coefficient
Multicomponent
by Verhoeven
the dimethoxynaphthalene
A-L-B
the
to a different
about
for electron
fluorescence
is quenched
again
on
lo493
is
across
is concerned,
constant
on
distance
mechanism. 24
systems
for
photoinduced
charge
separation.
In an A-L-B
components
too
(dyad),
short-lived
strategy
system,
i.e.
the photoinduced
to be
useful
the
number
pentads131,132
the
photosynthetic
For
reaction
importance
photosynthetic
transfer
purposes,
together
by
sequence
purposes.
charge separation
is to
Several
tetrads18.20,129-131
and
and
charge
of events
will
mimic
their
the function
development
the design
is
of
of
of artificial
connectors.
Pel)
amine (electron
As
separation
(rate
briefly
constants
discuss
the
triad
photosensitizers,
we
et aLI
acceptor,
photoinduced
few
by Wasielewski,
(electron
is usually
components.
This species
centre
separation
active
systems.
illustration
developed
of two
conversion
paramount
energy
molecular
and
made
charge
and long-lived
of
triads15.16.18.20,129-131
behavior
for
to obtain an efficient
increase
in a system
illustrated
process
for
quinone
(electron
donor,
Rel) linked
in
29,
involves
butyronitrile
Fig.
the
the
following
solutions):
(1)
lo494
V. BALZANI
h3
Ret'
Pel
T2
-A
I
0
1 /.....""""/,
...
...j."'
eW
:
.....'
/ ..
fj....."
, 14
1
1
o
diagram,
energy
bE
I/'
&,,hJ
Fig.29. Block
//i
molecular
and
srructure,
one-electron
role of photosensitizer
(Pel);
the quinone
plays the
donor,
respectively.
light
absorption;
(2) electron
s-l);
the
quinone
(l.lxlO*~
the
oxidized
porphyrin
the
design
efficient
charge
separation
illustrated
must
reaction
charge
(1.4~1010
a multicomponent
prevail
3
and
over
must
recombination
excited
prevail
over
reaction
29),
state
the
6 must
from
all
of
to
electron
decay
4,
to
the amine
to
since
be
back
electron
be
as slow
In
reaction
electron
trzinsfer
transfer
as
an
several
satisfied.
transfer
the
out that
performing
simple
have
porphyrin
be pointed
capable
at
the
excited
It should
requirements
(Fig.
the
s-1).
not
the
transfer
system
is
kinetic
example
from
(3) electron
of
thermodynamic
the
transfer
possible,
5,
the
and
Supramolecular
the converted
energy
photochemistry
reaction
occurs
compared
with
photosyntetic
the
reaction
performance
bacteria
where
of
-0.6
eV
multicomponent
supramolecular
of electron
systems.10~19
(bpy=2,2-bipyridine)
structures
configuration).
leads
electron
respect
The
center
produced
with
of
100%
are an electron
p-anisylamine
lie
on
(trans-type
on the Ru(trpy)22+
acceptor
).t35
( MV2+)
also
good
photosensitizers
building
where
the
in
M(bpy)s
up
of
components
where
are
to systems
species
components
based
transfer
the
geometry
to the photosensitizer
A triad
complexes
M(trpy),
on the contrary,
supramolecular
acceptor
Fig.30.
reaction
are
are relatively
(trpy=2,2:6,2-terpyridine).
to design
of the rate
the
However,
arrangement,
In the triad of
efficiency
10495
the
offers
complexes
the possibility
electron
opposite
donor
directions
configuration,
photosensitizer.
and an electron
and
with
Fig. 30). In
A and
donor
D
(di-
V. BALVWI
10496
addition,
do
M(trpy)2
not
lead
complexes
to
isomeric
substituted
M(bpy),
dyads
triads
and
bearing substituents
mixtures
contrary
systems.134
illustrated
Detailed
in
Fig.
at the 4-position
to
their
equivalent
investigations
30
have
on
been
the
recently
performed.l35$136
7.3
Polynuclear
metal
The possibility
transfer
useful
the
of governing
in supramolecular
of photochemical
of
light absorption
for
a specific
complexes
appear
to
energy
that
be particularly
of
devoted
to
exhibit
electronic
site (antenna
a variety
is presently
systems
towards
of electronic
much activity
multicomponent
channeled
harvesting
devices
Therefore
light
the direction
arrays
molecular
functions.137
synthesis
complexes
excitation
effect).
useful
extensive
can be
Transition
building
metal
blocks
for
polynuclear
synthetic
metal
strategy
complexes
of desired
nuclearity
of both
the metal
(L) in the
reaction
M+
nL
-->
M(L),
(29)
by
chelating
and
chemical structure.
in the place
a synthetic
easily
mono-
replaceable
or
ligands,
oligonuclear
sites (complexes
complexes
complexes
that
contain
free
as ligands
strategy).
7.3.1
Trinuclear
Using
possible
metal
the tripod-type
complexes
of tripod-type
bipyridine
ligands
shown
bipyridine
ligands.
in Fig.
31, it is
trimetallic
each metal-based
complexes
as
unit exhibits
Supramolecular photochemistry
Fig.31. Tripod-type
Fig.32. Trimetallic
tris-bipyridine
complexes
of
the
lo497
ligands.138
tripod-type
ligands
its
own
absorption
regardless
of
present
in
the
the
investigations,
electronic
decreases
number
energy
as
excited
and
and
transfer
expected
energy
show
of
in
takes
place
because
of
levels.
properties,
metal-based
units
structure.138
that
The
mixed-metal
from
Ru-based
relative
efficiency
which
links
that
are
Luminescence
the
the
in
138
electrochemical
type
supramolecular
however,
components,
lowest
spectrum
shown
complexes
to
OS-based
position
of
energy
the three
arms
of
their
transfer
of the
10498
V. BALZANI
tripod
the
ligand
increases.
compounds
energy
with
transfer
transfer
Detailed
larger
investigations
spacers
there
and conformers
where
where
energy
is very fast.
7.3.2 Polynuclear
ligands.
The
synthetic
complexes
complexes
strategy
has
synthesis
of polynuclear
as metal
ions,
as 2,3-
and
2,3-
as metals
revealed
with
nuclearity
metals,
bridging
obtained.*39-14s
tridecanuclear
schematic
The
compounds
view
of
the
Ru(II)
(BL).
(biq) as terminal
between
ligands,
containing
ligands
and
2 and
structural
the
Os(I1)
(abbreviated
2,2-bipyridine
ligands
the
different
have
been
decanuclear
and
of
@=@
OS2
L=Q-Q
by
biq
Q+-o
23 - dpp
Fig.33. Components
and/or
13, containing
of
are illustrated
and
for
terminal
syntheses
as ligands
successful
2,5-bis(2-pyridyl)pyrazine
bridging
bridging
and complexes
particularly
complexes
and/or
2,5-dpp)
of the bis(2qyridyl)pyrazine
of the polynuclear
complexes.
decanuclear
10499
Supramolecular photochemistry
Fig.34
Synthesis
of a decanuclear
compound.143
L
BL
b-
BL
BL
BL
BL
BL
BL
1:3
LwBLB$BLBLyL
4
Bt
P-
e;
BL
BL
Fig.35.
These
polynuclear
properties
and
including:
visible
nuclear
region
of a tridecanuclear
Synthesis
complexes
(i)
very
(E = 133000
intense
compound.145
several
absorption
interesting
bands
in
the
uv
Ru((~-2,3-dpp)Ru(bpy)(~-2,3-dpp)Ru[(~-2,3-dpp)Ru-
(ii) luminescence
at 77 K and
at room
electrochemical
each
exhibit
M-1 cm-t
ligand
concerned,
in
fluid
behaviour
can
the
solution
(each
be
reduced).
interest
of these
metal
As
both
temperature;
center
far
compounds
as
lies
can
in rigid
(iii)
be
energy
on the
matrix
a very
rich
oxidized
and
collection
is
fact
that
the
10500
V. BALZANI
Fig.36.
site
containing
controlled.
energy
the
Schematic
the
Each
levels
the
be
predetermined
in
the
in fact,
which
in
the
choice
the
be synthetically
of
same
by its
of the metal
units),
and
the
energy
blocks
transfer
bridging
and
array
building
ligand
own
of
the position
supramolecular
Exoergonic
share
can
is characterized
by the nature
units
a suitable
compound.143
state
by the surrounding
reaction.
units
can
used
between
takes
place
efficiency.
In the
shown
by
excited
mainly
metal-based
synthetic
metal-based
transfer
block,
slightly
various
100%
energy
building
and
of
been
lowest
(determined
ligands,
with
view of a decanuclear
case
possible
can
in Fig.
of the
to
be
design
tetranuclear
species
predetermined
compounds,
where
according
for example,
the
direction
to
the
of the decanuclear
of
four
it has
energy
patterns
compounds,
six
10501
Supramolecular photochemistry
A
v
A
Lc,4c~Md
y(
AA
La
(
r/>
Lav
Ma
(i)
BLa
BL$Lb
Lc
Lti
Made-to-order
Fig.37.
transfer
(i)
(i i i)
control
of electronic : energy
of the direction
in tetranuclear
(iv)
compounds:
L=bpy.
different
energy
complexes
migration
Because
redox
groups,
polynuclear
point
of
patterns
the
been
shown
presence
and
centres,
complexes
of view
investigations
have
of
intervalence
multielectron
transfer
an
the
transfer
and
fields
ordered
array
catalysis.
exhibit
the
of chromophoric
luminescent
interest
its
of
centres,
not
only
applications,
photo-,
electrochemistry,
transfer,
which
38.143
potentially
electrochemiluminescence,
chemistry,
in Fig.
are of outstanding
of energy
in
synthesized
but
these
from
the
also
for
chemi-,
and
spectroelectro-
photosensitization,
and
V. BAUANI
10502
4
Fig.38.
Schematic
in
the
representation
decanuclear
exoergonic
Ruz+
positions,
circles
components,
the
energy
compounds.
energy
indicate
of
transfer
and
steps.
Os2+,
and
arrows
Empty
respectively.
squares
respectively.
The
transfer
The
indicate
indicate
and
In
full
the
M(bpy),
bridging
processes
the
circles
peripheral
and M(biq),
ligands
are
2,3-dpp
in all cases.l43b
8.
A photon
information.
used
for
obtained
is at the same
The
interaction
energy
or
depend
on
simplest
form
Conclusion
time
of light
information
the
a quantum
with
matter
purposes.
degree
of
of energy
and a bit of
can
The
results
organization
of
therefore
be
that
be
the
can
receiving
matter.
The
atoms
in a molecule.
cause
simple
acts,
of organization
The
such
interaction
as
is that
of a small
of photons
a change
in
the
with
number
molecules
molecular
of
can
structure
10503
Supramolecular photochemistry
which
(isomerization),
energy
and information
converted
in
(and
norbornadiene
laser
spiropyran
can
number
stored
write
level
forces
of
or
bonds.
by
types
luminescence
spectrum,
it
is
possible
integrated
of elaborating
complex
perform
light
the
into
molecular
can be
isomer,149
and
information
on
by
hydrogen
components
carry
the
prefabricated
light-related
state
and
organized
molecular
energy,151
lifetime,
etc. That is,
and
functionally
devices)l37a
information
(light
bonds,
by covalent
desired
excited
(photochemical
species.
intermolecular
to put together
structurally
energy
of a discrete
input
photons
to
of
collection
of
of
capable
information
in a
and
of a supramolecular
sometimes
structure
of the various
current
a positive
excited
electrical
geometrical
refine
both
transforming
supramolecular
interactions,
spectrum,
functions
Interrogation
important,
of
attained
it is possible
to design
systems2
be
molecular
that
absorption
bits
to yield
(coulombic
components
properties:
by
is the assembly
can
together
By these routes
molecular
solar energy
energy
erase)
for
molecules.150
components
linking
principle,
quadricyclene
also
organization
various
chemical
energy
(and
in
For example,
of organization
of molecular
Supramolecular
exploited,
as)
higher
photochromic
A higher
be
purposes.
in its
beams
etc.)
can
pieces
components.
theories
feedback
unique,
species
by photon
of
can yield
information
of reciprocal
on
perturbation
of chemical
reactivity
and spectroscopy
its
and
with
supramolecular
systems.
Research
in the
area
of supramolecular
photochemistry
of molecular
are,
however,
photochemistry
at
very
and
early
reached in the
supramolecular
stage
of
has
chemistry.
development
of
V. Bm
supramolecular
structures
photochemistry.
that
investigations
have
photochemical
and
research
investigations
group.
Therefore,
photochemists
supramolecular
chemical
fact,
the
supramolecular
object
of
photochemical
with those
already
systems).
It should
is
required
activity
is sufficiently
the photochemical
supramolecular
for
of synthetic
the
photochemical
consolidated,
behavior
it will
be possible
to
of macroscopic
assemblies
of
Acknowledgment.
the light-induced
molecular
della Pubblica
of
which
for
chemists
development
Gubellini
also be
photochemistry.
photochemistry
processes
available
syntheses
strict collaboration
explore
the
(this is particularly
pointed
been
In
devices
interfacing
world.
the drawings.
Istruzione
II is gratefully
Financial
and Progetto
support
Finalizzato
from
the Minister0
acknowledged.
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