Narcis Avarvari MOLTECH-Anjou, UMR 6200 CNRS ......Narcis Avarvari MOLTECH-Anjou, UMR 6200 CNRS - University of Angers, FRANCE Chiral molecular electroactive precursors and conductors

Narcis Avarvari

MOLTECH-Anjou, UMR 6200 CNRS - University of Angers, FRANCE

Chiral molecular electroactive precursors and conductors

Conferinţa Diaspora în Cercetarea Ştiinţifică şi Invăţământul Superior din România Timisoara, 25-28 April 2016

Current research topics in the group 1. Chirality in tetrathiafulvalenes (TTF)

2. Electroactive ligands: TTF-Py, -phosphines, -Ox,-triazoles - multifunctional materials - enantioselective catalysis

3. Covalent donor-acceptor compounds

4. Multifunctional ligands

Coord. Chem. Rev. 2009, 253, 1398. Coord. Chem. Rev. 2010, 254, 1523. Inorg. Chem. 2012, 51, 8545. Chem. Eur. J. 2012, 18, 16097. CrystEngComm 2014, 16, 6612.

Chem. Eur. J. 2009, 15, 380. Inorg. Chem. 2013, 52, 5023.

N N

N S

S

S

S

MeO

OMe

CrystEngComm 2012, 14, 3096. Inorg. Chem. 2014, 53, 2708.

Chem. Eur. J. 2013, 19, 2504. Org. Biomol. Chem. 2015, 13, 1040.

Dalton Trans. 2015, 44, 8855.

Chem. Commun. 2016, feature art.

Outline 1. Introduction: tetrathiafulvalenes and chirality

4. Conclusions and outlook

3. Helical chirality in conducting crystals

2. Supramolecular helical chirality

++

+

+

- -

-

-

++++

+

-

-

-

0

0

0

0

0+

+

+++++

+

+

- -

-

-

+

++++

+

+

-

-

-

• crystallization in the presence of anions

Tetrathiafulvalene (TTF) and Derivatives

S

S S

S S

S S

S

+-e

-

+e-

S

S S

S

+ +-e

-

+e-

Electrocrystallization Chemical oxidation

salts and charge transfer compounds with conducting and/or magnetic propertiesdetermined by the solid state organization

E1/21 = 0,33 V E1/2

2 = 0,71 V

organic-inorganic segregation

mixed valence

HOMO TTF and SOMO TTF+•

Pt electrode

Strong interactions

metals (superconductors)

Weak interactions (paramagnetic dimers)

insulators or semiconductors

HOTTF HOTTF +.

N OM2 OM

¾ filled band

Metallic character

Mixed valence systems

Energy band formation

Interactions between radicals

HOTTF +.

HOTTF +.

Diamagnetic dimers

insulators

Fully oxidized systems

Fermi level

TTF-TCNQ an organic metal

TTF Eox = 0.33 V

TCNQ Ered = 0.17 V

TTFδ+-TCNQδ-

Chemical oxidation

Peierls distortion

J. Ferraris, D. O. Cowan, V. Walatka Jr, J. H. Perlstein, J. Am. Chem. Soc. 1973, 95, 948.

1D conductor

Metallic conductivity

incommensurate charge transfer degree

E

O p/b

k

kF = 0.295 p/b

EF

TTF TCNQ

Band diagram

(TM-TSF)2X (X = PF6-, ClO4

-, ReO4-) :a series of superconducting salts

D. Jérome, A. Mazaud, M. Ribault, K. Bechgaard, J. Phys. Lett. 1980, 41, L195. K. Bechgaard et al., J. Am. Chem. Soc. 1981, 103, 2440.

The Bechgaard salts Electrocrystallization

Supramolecular chemistry (rotaxanes and catenanes)

Dendrimers

OFET

Crystalline conductors and superconductors

Conducting polymers

NLO materials

Organic magnets

Langmuir-Blodgett

Catalysis

Solid state Solution

Modulation of physical properties (fluorescence)

Electrochemical sensors

TTF

Tetrathiafulvalene (TTF) and Derivatives

J.-I. Yamada, TTF Chemistry: Fundamentals and Applications of Tetrathiafulvalene, Springer-Verlag, 2004. J. L. Segura, N. Martin, Angew. Chem. Int. Ed., 2001, 40, 1372. D. Canevet, M. Sallé, G. Zhang, D. Zhang, D. Zhu, Chem. Commun., 2009, 2245.

III. Chiral redox active ligands for enantioselective catalysis

The control of the metal complexes reactivity upon oxidation - reduction

Influence on the catalytic processes?

substitutionally inert redox-switchable ligands redox-switchable hemilabile ligands

C. A. Mirkin et al. Angew. Chem. Int. Ed. Engl. 1998, 37, 894

Chiral tetrathiafulvalenes - Interests

II. Chiroptical redox switches, chiral recognition

I. Synthetic challenge

IV. Chiral molecular conductors

Chiral molecular conductors

Influence on the conducting properties

S

S

S

S

S

SN

OCH3

EDT-TTF-Me-oxazoline

racemic, R and SJ. Am. Chem. Soc. 2005, 127, 5748.

TTF-OX

Chem. Eur. J. 2010, 16, 528.

Multifunctional materials 1. Optical activity + Electrical conductivity

2. Enantiopure forms are inherently less disordered in the crystalline state

Chiral SWNT Krstić, Rikken et al. J. Chem. Phys. 2002, 117, 11315

Electrical resistance R D/L(I,B) = R0 {1 + b B2 + cD/LI•B} cD = - cL

handedness of the chiral conductor

eMChA effect (very weak) R (H, I) # R (H, -I)

3. Reports by Rikken et al. on electrical magneto-chiral anisotropy (eMChA) effects

4. Superconductivity in non-centrosymmetric systems R. Roy, C. Kallin, Phys. Rev. B 2008, 77, 174513.

need of a library of chiral precursors in which the chiral information is addressed in different ways

Chirality 2013, 25, 466.

C12H25

C12H25

OR

OR

83 R =

(S)-84 R =

(R)-84 R =

OO

O

O

O

O

O

O

Hexabenzocoronenes

SEM image

T. Yamamoto, T. Fukushima, A. Kosaka, W. Jin, Y. Yamamoto, N. Ishii, T. Aida, ACIE 2008, 47, 1672.

1. Supramolecular chirality

Using a C3 symmetric platform

helical chirality

propeller like conformation

O

O

O

O

O

O

O O O O O

O O O O O

O O O O O

R =

C3 symmetric tetrathiafulvalenes

O

O

O

R

O

NH

N

NHN

R

OHN

N

N

NH

RO

NH

NN

HN

p-p stacking hydrogen bonds

A. R. A. Palmans, J. A. J. M. Vekemans, E. E. Havinga, E. W. Meijer Angew. Chem. Int. Ed. Engl. 1997, 36, 2648 L. Brunsveld, H. Zhang, M. Glasbeek, J. A. J. M. Vekemans, E. W. Meijer J. Am. Chem. Soc. 2000, 122, 6175. J. van Gestel, A. R. A. Palmans, B. Titulaer, J. A. J. M. Vekemans, E. W. Meijer J. Am. Chem. Soc. 2005, 127, 5490.

Preferential helical twist induction R chiral group

Introduction of TTF units

C3 symmetric TTFs: convergent synthesis

S

S S

S

S ZnS

SS

S

S

2-

R Br S

SS

S

S

R

R

S

S CO2Me

CO2Me

O

P(OMe)3 S

S

S

SS

S

R

R

CO2Me

CO2Me

3. (COCl)2

1. LiBr2. LiOH·H2O

S

S

S

SS

S

R

R

COCl

O

O

O

S

S

S

SS

S

O

NN

NN

R

R

S

SS

S

S

S

ON

N

N

N

R

SS

SS

S

S

O

N

NN

N

RR

R

H

H

H

H

H

H

COCl

COCl

ClOC

85%

NH2

N

N

NH2

S

S

S

SS

S

O

NH

N

NNH2

R

R

80%

R, R = -CH2CH2 -

R = -CH3

R = -C2H5

R =

R =

R=

I. Danila, F. Riobé, J. Puigmarti, A. Pérez del Pino, J. D. Wallis, D. Amabilino, N. Avarvari, J. Mater. Chem. 2009, 19, 4495.

I. Danila, F. Riobé, F. Piron, J. Puigmartí-Luis, J. D. Wallis, M. Linares, H. Ågren, D. Beljonne, D. B. Amabilino, N. Avarvari, J. Am. Chem. Soc. 2011, 133, 8344.

S R

Introduction of chiral TTF units

250 300 350 400 450 500 550 600

-50

-40

-30

-20

-10

0

A

(m

de

g)

(nm)

initial signal

250 300 350 400 450 500 550 600

-50

-40

-30

-20

-10

0

A

(m

de

g)

(nm)

initial signal

60°C

250 300 350 400 450 500 550 600

-50

-40

-30

-20

-10

0

A

(m

de

g)

(nm)

initial signal

60°C

20°C

10 20 30 40 50

-60

-50

-40

-30

-20

-10

0

A

(m

de

g)

time (min)

CD spectra and evolution of the signal at 387 nm in dioxane

Supramolecular chirality

Temperature dependent circular dichroism measurements

C = 2x10-5 M


CW

CW CCW

CCW

Molecular Mechanics and Molecular Dynamics simulations

helical pitch 8°

Estab = 104.8 kcal/mole Estab = 106.8 kcal/mole M. Linares, KTH Stockholm, Sweden

Formation of fibres: first hierarchical level

d = 43 Å

The stabilization energy per molecule: Estab = (nEisol – Estack)/n

M helicity in solution for the primary fibers!

Mesoscopic size fibres in the solid state

Optical images

O

O

O

S

S

S

SS

S

O

NH

N

N

HN

S

SS

S

S

S

OHN

N

N

NH

SS

SS

S

S

O

NH

NN

HN

(S,S,S,S,S,S)

P helicity !


A sensitive system

SEM images Obtained with a heatgun Obtained with a hotplate

Microcroissants ! Fibres

I. Danila, F. Pop, C. Escudero, L. N. Feldborg, J. Puigmartí-Luis, F. Riobé, N. Avarvari, D. B. Amabilino, Chem. Commun. 2012, 48, 4552.

SEM image

250 300 350 400 450 500 550 600

-200

-150

-100

-50

0

50

100

150

200

A

(m

de

g)

(nm)

R enantiomer

S enantiomer

Supramolecular chirality

M helicity (R,R,R,R,R,R) enantiomer

CD measurements


The racemic system

SEM images 2 mg/ml


Amphiphilic systems

Odd-even effect

CW CCW

Estab = 131.3 kcal/mole Estab = 130.6 kcal/mole

Amphiphilic systems

(S) M helicity

(R) P helicity

M

P

Inversion

P

M

M

M

P

M

M

MEK:THF 9:1 MEK

M: 66%; P: 8%; M+P: 18%; not defined: 8%

F. Pop, C. Melan, I. Danila, M. Linares, D. Beljonne, D. B. Amabilino, N. Avarvari, Chem. Eur. J. 2014, 20, 17443.

Current directions in the C3 systems

T.-L. Lai, F. Pop, C. Melan, D. Canevet, M. Sallé, N. Avarvari, Chem. Eur. J. 2016, 22, 5839

Pyrenes Luminescent donor-acceptor organogels

65 mg/mL (C2H2Cl4)

exc = 344 nm (C2H2Cl4) exc = 405 nm (C2H2Cl4) TCNQ

8 mg/mL (C2H2Cl4)

bipy bipy

{Pyr-Pyr}*

exc = 344 nm (C2H2Cl4)

bipy {Pyr-TCNQ}*

2. BEDT-TTF related donors with stereogenic carbon atoms

J. D. Dunitz, A. Karrer, J. D. Wallis, Helv. Chim. Acta, 1986, 69, 69.

J.-P. Griffiths, N. Hui, R. J. Brown, P. Day, J. D. Wallis, Org. Biomol. Chem., 2005, 3, 2155.

Only few examples of conducting salts with the simply methylated ETs and no complete series

(S,S,S,S) 2:1 semiconducting salts with XF6– (S,S,S,S) 3:2 metallic salts with BF4– and ClO4–

A. Karrer, J. D. Wallis, J. D. Dunitz, B. Hilti, C. W. Mayer, M. Bürkle, J. Pfeiffer, Helv. Chim. Acta 1987, 70, 942.

J. S. Zambounis, C. W. Mayer, K. Hauenstein, B. Hilti, W. Hofherr, J. Pfeiffer, M. Buerkle, G. Rihs, Adv. Mater. 1992, 4, 33.

(S,S) 2:1 superconducting salt with ClO4– below 2K under 5 kbar (S,S,S,S) (TM-ET)x[MnCr(ox)3] metallic ferromagnet

J. R. Galán-Mascarós, E. Coronado, P. A. Goddard, J. Singleton, A. I. Coldea, J. D. Wallis, S. J. Coles, A. Alberola, J. Am. Chem. Soc. 2010, 132, 9271.

J. D. Dunitz, A. Karrer, J. D. Wallis, Helv. Chim. Acta 1986, 69, 69. S. Matsumiya, A. Izuoka, T. Sugawara, T. Taruishi, Y. Kawada, Bull. Chem. Soc. Jpn. 1993, 66, 513. F. Pop, S. Laroussi, T. Cauchy, C. J. Gómez-García, J. D. Wallis, N. Avarvari, Chirality 2013, 25, 466.

Synthesis of chiral methylated TTFs

Orthorhombic P212121 a=9.1424(6) Å b=11.0497(5) Å c=13.7839(11) Å V=1392.46(16) Å3

(S,S) (R,R) Racemic

I3- 1:1, P1 1:1, P1 1:1, P-1

PF6– 2:1, P21 2:1, P21 2:1, P-1

ClO4– , ReO4

– 2:1, P6222 2:1, P6422 1:1, P21/c

DM-EDT-TTF

Me-axial

Monoclinic P21 a=13.147(1) Å b=15.675(3) Å c=15.485(2) Å β=107.286(10)° V=3047.07(70) Å3 Z=4

(S,S) (R,R) Racemic

PF6– 2:1, P21 2:1, P21 2:1, P-1

(R,R), (S,S) and racemic (DM-EDT-TTF)2PF6 Triclinic P-1 a=6.666(4) Å b=8.384(8) Å c=15.221(1) Å α=86.281(8)° β=77.464(7)° γ=67.141(6)° V=765.03(13) Å3 Z=1

Me-eq

(R,R), (S,S) (DM-EDT-TTF)2PF6

Semiconducting

Me-eq

racemic (DM-EDT-TTF)2PF6

σ = 250 S cm-1 at 295 K

b intrastack 0.7769/0.6498 eV

b interstack 0.0599/0.0301/ 0.0645 eV

Pseudo-1D-metal at r.t.

No structural change at 100 K solutions with ee of 50% provide both phases

F. Pop, P. Auban-Senzier, A. Frąckowiak, K. Ptaszyński, I. Olejniczak, J. D. Wallis, E. Canadell, N. Avarvari, J. Am. Chem. Soc. 2013, 135, 17176.

From stereogenic centers to enantiomorphic crystals

Hexagonal P6222 a = 7.2053(4) Å c = 48.639(7) Å V = 2186.85(40) Å3 Z=3

(S,S) (R,R)

ClO4– 2:1, P6222 2:1, P6422 S·····S contacts (Å )

Me-eq

(DM-EDT-TTF)2ClO4

Me-axial

(R,R) and (S,S)-(DM-EDT-TTF)2ClO4 b intrastack 0.4031 eV

b interstack 0.2090 eV

Open Fermi surface

Metallic conductivity

(R,R) and (S,S)-(DM-EDT-TTF)2ClO4

F. Pop, P. Auban-Senzier, E. Canadell, G. L. J. A. Rikken, N. Avarvari, Nature Commun. 2014, 5:3757, DOI:10.1038/ncomms4757.

First evidence for the eMChA effect in a bulk chiral conductor

(R,R) (S,S)

ΔR/RIB = −0.6 10−2 T−1A−1 ΔR/RIB = +0.6 10−2 T−1A−1

/ / 2

0( ) (1 )D L D LR R B b B,I B I

ΔR(I, B) ≡ R(I, B) – R(–I, B)

/2 D LR

R

B I

=VeMChA /2GRBI2

G is a preamplifier gain

(R,R) and (S,S)-(DM-EDT-TTF)2ClO4

D/L D/L 2

0ˆ( ) (1 )R R B b B,J B J

/ / 2

0( ) (1 )D L D LR R B b B,I B I

F. Pop, P. Auban-Senzier, E. Canadell, G. L. J. A. Rikken, N. Avarvari, Nature Commun. 2014, 5:3757, DOI:10.1038/ncomms4757.

(R,R)

(S,S)

CONCLUSIONS and OUTLOOK

2. TM-BEDT-TTF, DM-BEDT-TTF, DM-EDT-TTF

- first evidence for the eMChA effect in a bulk chiral conductor

- complete series of chiral conducting salts

- inverse magneto-chiral anisotropy

- spin filtering

1. C3-symmetry and supramolecular chirality

- electroactive organogel and conducting nanofibers

- formation of homochiral helical fibers

- induction of chirality: non-linear effects

- tuning the helical pitch and the solubility

- conducting fibers

Acknowledgements

Dr. Ion Danila

Dr. Loan Lai

Dr. Flavia Pop

Dr. Caroline Melan Dr. Cristina Oliveras

Dr. David Canevet, Prof. Marc Sallé: pyrene organogels

Dr. François Riobé

Acknowledgements

Collaborations

Dr. E. Canadell ICMAB, Barcelona Band structure calculations

Dr. P. Auban-Senzier LPS, Univ. d’Orsay Conductivity measurements

Dr. G. L. J. A. Rikken LNCMI, Toulouse eMChA effect

Dr. D. Amabilino Univ. of Nottingham, UK C3 systems

Dr. M. Linares Dr. D. Beljonne Univ. of Mons, Belgium

MM and MD calculations CD calculations

Univ. of Linköping, Sweden

Dr. J. Crassous Univ. of Rennes 1, France helicenes

Dr. N. Vanthuyne Univ. of Marseille, France chiral HPLC

Documents

Narcis Avarvari MOLTECH-Anjou, UMR 6200 CNRS ......Narcis Avarvari MOLTECH-Anjou, UMR 6200 CNRS - University of Angers, FRANCE Chiral molecular electroactive precursors and conductors