LINZ LECTURES Lecture 1. The Development of Organic ... · Lecture 1. The Development of Organic Conductors: Mtl S d t dS i d tMetals, Superconductors and Semiconductors Lecture 2ALecture

LINZ LECTURES

Lecture 1. The Development of Organic Conductors: M t l S d t d S i d tMetals, Superconductors and Semiconductors

Lecture 2A Introduction and Synthesis of ImportantLecture 2A. Introduction and Synthesis of Important Conjugated PolymersLecture 2B. Solid State Polymerization

Lecture 3. Fullerene ChemistryLecture 3B Molecular EngineeringLecture 3B. Molecular Engineering

1

Solid State PolymerizationSolid State PolymerizationLinz, June 10, 2008

P l di t lPolydiacetylenes

PolythiazylPolythiazyl

PEDOT Br3PEDOT Br3

2

Solid State PolymerizationP l di t lPolydiacetylenes

R R

Rhν

or Δ

R

nor Δ

R

R

R

R

R

R

h

R

R

R R

R

R

R

R

hνor Δ R

R

R

RR

n

R

R

R R

R

R

R

R

R

R

3C C

R

R

C C

R

R

"Spontaneous"

4Wegner, G. in Molecular Metals, Hatfield, W. E. Ed. NATO Conference Series VI: Materials Science, Vol. 1, Plenum, 1979.

S h tt M J Ph Ch B 2006 110 15864

5

Schott, M J. Phys. Chem. B 2006, 110, 15864

Wegner, G. in Molecular Metals, Hatfield, W. E. Ed. NATO Conference Series VI: Materials Science, Vol. 1, Plenum, 1979.


R

n

Large distortion

Rn





PEDOT Br3PEDOT Br3

8

Polythiazyl (SNx)Polythiazyl (SNx)

S2N2 SNx

9

M. J. Cohen, A. F. Garito, J. Heeger, A . G. MacDiarmid, C. M. Mikulski, M . S. Saran, J.

10Street, G. B.; Gill, W. D. The chemistry and physics of polythiazyl, (SN)x, and the polythiazyl halides. NATO Conference Series VI: Materials Science (1979), Volume Date 1978, 1(Mol. Met.), 301-26.

M. J. Cohen, A. F. Garito, J. Heeger, A . G. MacDiarmid, C. M. Mikulski, M . S. Saran, J. Kleppinger J. Am. Chem. Soc. 98, 1976 3844.

11M. J. Cohen, A. F. Garito, J. Heeger, A . G. MacDiarmid, C. M. Mikulski, M . S. Saran, J. Kleppinger J. Am. Chem. Soc. 98, 1976 3844.

12M. J. Cohen, A. F. Garito, J. Heeger, A . G. MacDiarmid, C. M. Mikulski, M . S. Saran, J. Kleppinger J. Am. Chem. Soc. 98, 1976 3844.

Electron micrograph of a smooth area of an SN Cr stalElectron micrograph of a smooth area of an SNx Crystal

13Geene R.L.; Street G.B.,Proceedings of the NATO-ASI on Chemistry and Physics ofOne-Dimensional Metals, Bolzano, Italy, August 1976. (Edited by KELLER H.). Plenum Press, New York (1977)

14Geene R.L.; Street G.B.,Proceedings of the NATO-ASI on Chemist,y and Physics ofOne-Dimensional Metals, Boizano, Italy, August 1976. (Edited by KELLER Hi.). Plenum Press, New York (1977)

First and Only Superconducting Polymer

15Geene R.L.; Street G.B.,Proceedings of the NATO-ASI on Chemist,y and Physics ofOne-Dimensional Metals, Boizano, Italy, August 1976. (Edited by KELLER Hi.). Plenum Press, New York (1977)




PEDOT Br3PEDOT Br3

16

Traditional Synthetic Methods of PEDOT

OO OO

S

OOFeCl3/CHCl3 or CH3CN

or Electrochemical Polymerization S

OO

nS

PEDOTEDOT

OO OOPSS

Na2S2O8/H2OPEDOT-PSS

S

17Meng, H.; Perepichka, D.F.; Wudl, F. Angew. Chem. Int. Ed., 2003, 42(6), 658-661

Traditional Synthetic Methods of PEDOT

O ONi(0) cat.

O O

S S nX X

X = Br ClX = Br, Cl

18

PEDOT via Solid statePEDOT via Solid-state Polymerization

Å O OÅ

S nn

19

A Facile Solid-state Synthesis of PEDOT

O O

X XHeat

O O

SX X SSP S nX = Br, I

60 oC, 8 h.

OOOO

,

S nS

BrBr

OO

20Meng, H.; Perepichka, D.F.; Wudl, F. Angew. Chem. Int. Ed., 2003, 42, 658.

Non Polymerizing Melt

QuickTime™ and aH.264 decompressor

are needed to see this picture.

(120 ti f t th th l ti )21Ramp to 100 oC, heat 100-150 oC at 10 deg/min, hold 150 oC, total time 100 min

(120 times faster than the real time)

Microscopy of Solid State Polymerization

QuickTime™ and aH.264 decompressor

are needed to see this picture.

(480 times faster than the real time) (240 times faster than the real time)

Hold at 87 oC, 1 h Hold at 92 oC, 1 h

22

T lTwo year sample

23

A Facile Solid-state Synthesis of PEDOTPEDOT

---UV-vis-NIR

1.00

1.20

0.80

tion

0.40

0.60

Abs

orpt

760 nm (1 63 eV)

0.20

0.40

As synthesized filmAfter dedoping with hydrazine monohydrate

760 nm (1.63 eV)

0.00300 800 1300 1800 2300

Wavelength (nm)

24

Wavelength (nm)


-2.00

PEDOT---Electrochemistry CV

-1.00+ 0.17 V

E onset 0 40V

0.00(mA

)

Eoxaonset = - 0.40V

1.00

Cur

rent

- 0.52 VEredonset = - 2.05 V

2.00

C E g = 1.65 eV

3.00-3.00 -2.00 -1.00 0.00 1.00

25

3.00 2.00 1.00 0.00 1.00

Potential (v.s. SCE)Potential (v.s. SCE)

A Facile Solid-state Synthesis of

25

PEDOT---FTIR

20

25

.)

SSP-PEDOT

15

nce

(a.u

.

a

FeCl PEDOT10

nsm

ittan

b

FeCl3-PEDOT

5Tran

045095014501950245029503450

W l h N b ( 1)26

Wavelength Number (cm-1)


---13C NMR

13

13 SSP-PEDOT

2CP-MAS Solid 13C-NMR

2CP-MAS Solid 13C-NMR

1OO1 1OO1

2

3

S

OO

n2

3

2

3

S

OO

n2

3

FeCl3-PEDOT

PEDOTPEDOT

27


Conductivity of solid-state polymerized PEDOT

FeCl3 polymerized

---Conductivity

Conductivity of solid-state polymerized PEDOT polymerized PEDOT

Sample a) A B C D 0-5 oC

Reaction time 2 years b) 24 h 4 h 24 h 24 h

Crystals / fibers 80 S/cm 33 S/cm 20 S/cm NA NA

Pellets as synthesized 30 S/cm 18 S/cm 16 S/cm 0.1 S/cm NA

Pellets after I2 doping 53 S/cm 30 S/cm 27 S/cm 5.8 S/cm 7.6 S/cm

Thin films NA 23 S/cm NA NA NA

Thin films after I2 NA 48 S/cm NA NA NA doping

a) Conversion temperature A = ca. 20 oC, B = 60 oC, C = 80 oC, D = 120 oC

28b) The monomer was stored in a closed jar for 2 years at room temperature (ca. 20 oC)


0.1

---Conductivity vs. Tempeature

Crystal

Polymer Crystal

0.01

m*m

)

Crystal

Fiber

0.001vity

(Oh Monomer

Crystal0.001

Res

istiv

0.00010 50 100 150 200 250 300 350

29Temperature (K)


O O

Br Br

---Monomer Crystal Packing

SBr Br

The closest neighboring Br - Br distance (3.45 Å) is shorter than the

sum of the Van der Waals radii (3.6 ---4.0 Å)

a = 25.27 Å, b = 5.01 Å, c = 15.67 Å

α 90 ο β 123 96 ο γ 90 ο

30

α= 90 ο, β = 123.96 ο, γ = 90 ο

Monoclinic

A Facile Solid-state Synthesis of PEDOT---Monomer Crystal Packing

O O

SI I

The closest neighboring I - I distance (3.73 Å) is shorter than the sum of Van ( )

der Waals radii (4.10 Å)

a = 11.43 Å, b = 4.90 Å, c = 15.93 Å

α= 90 ο, β = 96.40 ο, γ = 90 ο

31Monoclinic

A Facile Solid-state Synthesis of PEDOTO O

Cl Cl

---Monomer Crystal Packing

SCl Cl

The closest neighboring Cl - Cl distance (3 58 Å) is longer than thedistance (3.58 Å) is longer than the sum of Van der Waals radii (3.40 Å)

a = 5.11 Å, b = 7.80 Å, c = 20.31 Å

α= 90 ο, β = 93.75 ο, γ = 90 ο

32

α 90 , β 93.75 , γ 90

Monoclinic

A Facile Solid-state Synthesis of PEDOT---Conducting Thin Film Preparation

The average surface resistance:

Glass substrate: 2.1 x 103 Ω/ (Film thickness: 2700 Å)

Plastic substrate: 3.6 x 103 Ω/ (Film thickness: 1300 Å))

Surface conductivity: > 200 S/cm.

33

Other Thiophene Derivatives

S H J B id R C h D J W i ht S P Gil M M C ll h I C l S J

34

Spencer, H.J.; Berridge, R.; Crouch, D.J.; Wright, S.P.; Giles, M.; McCullough, I. Coles, S.J.; Hursthouse, M.B.; Skabara, P.J. J. Materials Chem. 2003, 13, 2075.

Conclusion

• PEDOT synthesized by solid-state polymerization (SSP)

• Polymerization appears to involve radical intermediates

• Monomer crystal packing favors the solid-state reaction cfDIEDOT and DBEDOT vs DClEDOT

• The reaction is first-order with Ea ca 27 kcal/mole

• The solid-sate polymerization can be applied to thefabrication of conducting thin films on insulating substrates

35• The solid-sate polymerization appears to be generally applicable to

electron rich dibromothiophenes

36

37

Monomer Synthesisy

O O O O

2) I2 - 78 oC, then RT 2 h

THF, RT then reflux 1 h1) 2.5 mole n-BuLi

O O O OS

S S IIDIEDOT

) 2 ,

O O

S

O O

S BrBrDBEDOT

NBS

CHCl3/AcOH5 - 10 oC, 8 h

O O O ONCS

CHCl /A OH

DBEDOT

S S ClClDClEDOT

CHCl3/AcOH5 - 10 oC, 8 h

38

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LINZ LECTURES Lecture 1. The Development of Organic ... · Lecture 1. The Development of Organic Conductors: Mtl S d t dS i d tMetals, Superconductors and Semiconductors Lecture 2ALecture