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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
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Voltage Effect
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Current Density Effect
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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