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Stimuli-Responsive Polymers for
Multifunctional Composites
Ian Manners
Inorganic, Macromolecular and Materials Chemistry Group
School of Chemistry
Organic Polymers
•cata
lysts
•ele
ctrode m
edia
tors
•photo
nic
mate
rials
•conductive m
ate
rials
•photo
conductive m
ate
rials
•lu
min
escent m
ate
rials
•sensors
•stim
uli
responsiv
e g
els
•m
agnetic m
ate
rials
•fa
brication o
f nanopattern
ed s
urfaces
•hie
rarc
hic
al self-a
ssem
ble
d m
ate
rials
•m
eta
lloenzym
e m
odels
•W
hitte
ll, G
.R. M
anners
, I.
“Metallopolymers -New Multifunctional Materials
”Adv Mater 2007, 19, 3439
•Schubert, U
.S.; M
anners
, I.; N
ew
kom
e, G
.R. (E
ds) AC
S S
ym
posiu
m S
eries (2006)Vol. 9
28
“Metal-Containing and Metallosupramolecular Polymers and Materials
”
Metallopolymers
Metallopolymers --New M
ultifunctional Materials
New M
ultifunctional Materials
Adv. Func. Mater.2002, 12, 415
Air (O
2) Pressure Sensor
•quenching of phosphorescence from excited triplet state
sid
e c
hain
meta
llopoly
mer
Hig
h p
ressure
Low
pre
ssure
-phosphore
scence inte
nsity d
istrib
ution
(fals
e c
olo
r)
dye
dye*
Quenched b
y O
2
Polyferrocenylsilanes (PFSs)
Poly(ferrocenylsilane)
PFS
Fe
Si
Me
Me
n
exam
ple
•Science2001, 294, 1664
main
chain
meta
llopoly
mer
Properties of PFS : Ceramic Precursors
Science, 2000, 287, 1460
> 500°C
PFS
ceramic
> 500°C
, N
2
Ordered Arrays of Magnetic Ceramic Nanorods via Nanoim
print Lithography
AAO
= n
anoporo
us A
nodic
Alu
min
ium
Oxid
e
Patterned M
agneticNanorods
Fe
SiMe
Me
Fe
Si
MeMe
n/2
Fe
SiMe
Me
Fe
Si
MeMe
n/2
Fe
SiMe
Me
Fe
Si
MeMe
n/2
E1/2
(1)
E1/2
(2)
++
+
Properties of PFS -Redox Control of Polymer Polarity
non-polar
polar
oxid
ize
reduce
A PFS gelw
ith a
sm
all
degre
e o
f cro
sslin
kin
g in a
highly polar solvent:
Neutral Fe(II)
Cationic Fe(III) and Neutral Fe(II)
expanded
contracted
SEM of a single scale of a Morpho rhetenor butterfly wing
Chara
cte
rized b
y fix
ed lattic
e s
pacin
g -
Bra
gg / s
top-b
and w
avele
ngth
and c
olo
r is
fix
ed
Natural Photonic Crystals : Opals and Butterfly W
ings
Natural Opals
Tunable lattice spacing = Tunable colour
Redox-Responsive Photonic Crystals Based on PFS Gels
blue
Oxidize or Reduce
Solvent Swollen Gel
red
Working Eletrode
Electrolyte/Solven
t
Modified C
ounter Electrode
Polymer G
el Photonic C
rystal
Broken
Circu
it
Application of a Voltag
e Bias
Positively Polarized W
orking Electrode
Site of Oxidation of PFS
Neg
atively Polarized C
ounter
Swelling of Composite
Upon O
xidation of PFS
Electrochemical Tuning
ITO w
orking electrode
Photonic Ink (P-ink)
Prototype Devices
500
600
700
0
10
20
30
40
50
Reflectivity (%)
Wavele
ngth
(nm
)
initia
l re
flecta
nce
reflecta
nce follo
win
g a
ppl. o
f 1.2
V for 2m
in
reflecta
nce follo
win
g a
ppl. o
f 1.4
V for 2m
in
reflecta
nce follo
win
g a
ppl. o
f 1.6
V for 2m
in
reflecta
nce follo
win
g a
ppl. o
f 1.8
V for 2m
in
Electrochemical Tuning of P-Ink
Num
ber of C
ycle
s
Bragg Peak (nm)
Photonic Crystal Displays using PFS Gels with Redox Tunable Swellability
1-s
ingle
MATE
RIA
L
RG
B +
near-
IR
Using Patterned Electrodes
Opalu
x Inc.
ww
w.o
palu
x.c
om
/
Nature Photonics,2007
1, 468
Features and Advantages of Photonic Ink (P-ink)
1. Full
colo
r dis
pla
y fro
m s
ingle
mate
rial fo
r lo
w m
ate
rials
and p
roduction c
ost.
2. M
eet sig
nage n
eeds in s
ize fro
m s
helf e
dge to h
ighw
ay b
illboard
s.
3. H
igh b
rightn
ess, peak reflectivity u
p to 9
5%
.
4. Low
pow
er consum
ption.
1. Low
voltage a
nd c
urrent during s
witchin
g.
2. M
inim
al pow
er consum
ption w
hen im
age is s
tatic.
5. Sub-s
econd s
witchin
g s
peed.
6. Applic
able
on rig
id o
r flexib
le s
ubstrate
s.
7. Lig
htw
eig
ht, rugged, dura
ble
, and d
am
age tole
rant.
8. C
osts
scale
s o
nly
lin
early w
ith s
ize.
Product under Development -
battery
charg
e indic
ato
r
ww
w.o
palu
x.c
om
Nature Photonics2007, 1, 468
Angew. Chem. Int. Ed.2009,48, 943
Summary
Summary
•Metal Centers can IntroduceInteresting Properties and Functions
-m
ultifunctional com
posites
•Stimuli-Responsive and Functional Materials:
-air p
ressure
sensors
based o
n p
hosphore
scence q
uenchin
g
-pre
curs
ors
to c
era
mic
s c
onta
inin
g m
agnetic a
nd c
ata
lytically
active n
anopartic
les
-re
dox-responsiv
e g
els
for photo
nic
cry
sta
l dis
pla
ys
EPS
RC
, EU
Marie C
urie C
hair, EU
Inte
rnational R
ein
tegra
tion G
rant,
EU
Marie C
urie P
ostd
octo
ral Fello
wship
Pro
gra
m, AW
E, Lanxess,
Spanis
h G
overn
ment PD
F P
rogra
m, D
FG
PD
F P
rogra
m,
Royal Socie
ty W
olfson R
esearc
h M
erit Aw
ard
, N
SER
C P
DF P
rogra
m,
Univ
ers
ity o
f Bristo
l Sta
rt U
p F
unds
FUNDING
COLLABORATIONS
Geoff O
zin
(Toro
nto
)
Mitch W
innik
(Toro
nto
)C
aro
line R
oss (M
IT)
Jennifer Lu (Agile
nt)
Tom
Russell
(U M
ass)
Ric
h S
ponta
k (N
C S
tate
)
ALL M
Y STUDENTS
Thanks for lis
tenin
g !
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