Ryan ChiechiProf. Miguel Garcia-Garibay

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The Development of Organic Conductors, Including Semiconductors,

Metals and Superconductors

Lessons from History, Continued

The Development of Organic Conductors, Including Semiconductors,

Metals and Superconductors

Lessons from History, Continued

Conjugated Polymers for Organic Electronics

Organic Superconductors

Organic Conductors andMetals

Se

Se

Se

SeElectrolysis

Trichoroethane/Bu4NXTMTSF2X

Bechgaard Salts

TMTSF

The First Organic Superconductors

Electrochemical Synthesis Apparatus

Actual Electrosynthesis

From Bechgaard, K and Jerome, D., Scientific American

Summary of Requirements for Organic Metals and Superconductors

Planar π-donors and/or acceptors

Segregated stacks of π-donors and/or acceptors

Partial charging of stacks of π-donors and/or acceptors

The End of the Stack Tyranny: the Kappa Phase

A Polymeric Anionic Layer

Buckminsterfullerene-Derived Solids

BEDT-TTF, etc superconductivity WITH magnetism

Other Organic Superconductors

Conjugated Polymers for Organic Electronics

Organic Conductors andMetals

Organic Superconductors

Organic Electronics: Organic Semiconductors

Polymeric Light Emitting Diodes (PLEDs)

Organic Light Emitting Diodes (OLEDs)

Organic Field Effect Transistors (OFETs, OTFTs)

Organic Memory Devices (OMDs)

Polymeric Electrochromics

Polymeric Photovoltaics (P-PVs)

Organic Semiconductors: Key Parameters

Semiconductor gap, Eg [E(π- π*)]

Relative LUMO vis a vis electrode material

Charge-carrier mobility (µ)

Processing and morphology

Relative HOMO vis a vis electrode material

Nature of the charge-carrier (h(+) or e(-))

Conjugated Polymers in 1987

The Most Popular Conjugated Polymers

n

X

Y

X = S, NH, NR; Y = H, R, Ph, etc

HN

n

S n

(CH)x

PPP

PA PANI

PITN

PT, PPy, etc

X

Y

Z

PPVs

X Y

n

PFs

O O

S nPEDOT

HH

H

H H

H

H H H H

HHHHHH

cis trans

The Two Configurations of PA

Optical Properties of Conducting Polymers. Patil, A. O.; Heeger, A. J.; Wudl, F. Chem. Rev. 1988, 88, 183–200

A BEA EB=

The Degenerate Ground State of PA

The Soliton Symmetry of a “Defect” in PA

The Neutral SolitonMaximum bond equalization

Optical Properties of Conducting Polymers. Patil, A. O.; Heeger, A. J.; Wudl, F. Chem. Rev. 1988, 88, 183–200

Ideal Real

"Insulator"

-e

Conductor

The Purported Coducting and Insulating States of Poly(acetylene)

Conductor

+e

Conductor

Conductor Conductor

Conductivity Through Bipolarons (Dications)

-e

-e

HN N N

HN

nH

H+

HN N N

HN

n

HN N N

HN

nH

HN N N

HN

nH H

H+

PolyanilineProton-Induced Spin Unpairing Mechanism

Another Proteochromic Compound

400 600 800 10000.0

0.2

0.4

0.6

0.8

1.0

Abs

orba

nce

(A.U

.)

λ

BF4 Salt Methyl Ether

RC3-22 Film

S

S

n

hex

hex

N

N

OMe

OMe

S

S

n

hex

hex

N

N

BF4

BF4

Ryan Chiechi

O

O

S

S

n

Polyphenylthiophene Ketone (PPTK)

Backbone Ketones for Robust n-Dopable Polymers

O

O

S

S

n

O

O

S

S

n

O

O

S

S

n

e

PEK and PEEK, high-performance polymers

O

O

*

O

n

Synthesis viaFriedel-Crafts Polymerization

Cl

Cl

HexMgBr

NiCl2[dppp]Et2OQY

O

O

S

S

n

hex

hex

hex

hex

I2

KIO3AcOH/H2SO4

reflux78%

hex

hex

I

I Pd[PPh3]4THF77%

S ZnCl

hex

hex

S

SAlCl3

10 wt % LiClCH2Cl2

Ph(COCl)p-2

Cation Formation

1) AlCl3CH2Cl2

2) NaOMe

O

O

S

S

n

hex

hex

N S

S

n

hex

hex

N

N

OMe

OMe

S

S

n

hex

hex

N

N

Aq. HBF4

BF4

BF4

Ryan Chiechi

Ketone Conversion

4000 3500 3000 2500 2000 1500 1000 50020

30

40

50

60

70

% T

rans

mitt

ance

cm-1

Poly Ether Poly Ketone

S

S

n

hex

hex

N

N

OMe

OMe

O

O

S

S

n

hex

hex

Ketone

Cation Formation

HCl Gas

NH3 Gas

S

S

n

hex

hex

N

N

OMe

OMe

S

S

C6H13

C6H13

O

On

Other Properties of the Poly(ketone)

Photophysics

Excitation at 77K

Excitation at 298K

In situ n-Doped Conductivity Measurement

n-Doping Spectroelectrochemistry

O

O

S

S

n

hex

hex

300 450 600 750 900 1050 1200 1350 1500 1650-0.05

0.00

0.05

0.10

0.15

0.20

Abs

(A.U

.)

λ

Potential (mv) 0 -1450 -1600 -1700 -1750 -1800 -1850 -1900

O

O

S

S

n

hex

hex

O

O

S

S

n

hex

hex

e

Possible Explanation of Conductivity as a Function of n-Doping

O

O

S

S

n

hex

hex

e

O

O

S

S*

n

hex

hex

O

O

S

S*

n

hex

hex

O

O

S

S* *

n

hex

hex

hex

xeh

Conclusions:

A high-performance, structural polymer is a robustn-dopable conducting polymer

n-Over “doping” creates a conductor from a Mott insulator

Finally Stereochemistry

Richard D. McCullough,' Renae D. Lowe, Manikandan Jayaraman, and Deborah L. Anderson J. Org. Chem. 1993, 58, 904-912

Richard D. McCullough, Stephanie Tristram-Nagle,Shawn P. Williams, Renae D. Lowevt and Manikandan Jayaramant J. Am. Chem. Soc. 1993,115, 4910-4911

Elena E. Sheina, Jinsong Liu,Mihaela Corina Iovu, Darin W. Laird, andRichard D. McCullough*Macromolecules 2004, 37, 3526-3528

Application of the GRIM Reaction

A. Bolognesi, G. Bajo, J. Palohemio, T. Oestergoerd, H. Stubb Adv. Mater. 1997, 9, 121-124

Elecrectroemission of Polarized Light

S

(CH2)10OCH3

n

QuickTime™ and aTIFF (LZW) decompressor

are needed to see this picture.

QuickTime™ and aTIFF (LZW) decompressor

are needed to see this picture.

Voltage Effect

QuickTime™ and aTIFF (LZW) decompressor

are needed to see this picture.

Current Density Effect

QuickTime™ and aTIFF (LZW) decompressor

are needed to see this picture.

Polarized Electroemmission!

Summary

Organic materials based on molecular solids give rise to properties such as metallic conductivity and superconductivity, usually associated with extended solids

Organic conjugated polymers are versatile scaffolds for the development of materials that exhibit a number of exotic properties