frontiers workshop design and synthesis of a molecular motor incorporating insulating fragments...
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Frontiers Workshop
Design and Synthesis of a molecular motor incorporating insulating
fragments
Guillaume Vives
PhD Supervisors : Gwénaël Rapenne and Jean-Pierre Launay
C. Joachim et al, Science 1998 , 281, 531-533
STM Images on Cu (100)
ESQC Calculations
Motionless
In rotation
ROTATION OF DECACYCLENE
A non-directional rotor
hexa-tert-butyl decacyclene
3
PRINCIPLE OF THE ROTARY MOTEUR
e-
_+
EG
EG
EG
EG
EG
Anode Cathode
Step 1
(Rotation of one fifth of turn)
_+
EG
EG
EG
EG
EG
Anode Cathode
Step 2
_+
e-
EG EG
Anode Cathode
EG
EG
EG
e-
Step 3
Desired behavior Unwanted mechanism
e-
+ _
EG
EG
EG
EG
EG
CathodeAnode
e- e-
+ _CathodeAnode
e-
EG
EG
EG
EG
EG
4
DESIGN
Stator : Tripodal ligand functionalized to be anchored to the surface. Rotor : Cp ligand with five rigid arms terminated by electroactive groups (EG) Insulating Spacers to prevent intramolecular electron transfer. Joint : Ruthenium atom
N
N
N
N
N
N
B
H
Ru
EG: Electoactive Group
Oxide Surface
EG
EG
EGEG
EG I
I
I
I I
I: Insulator
Four Parts :
5
GOAL MOLECULE
Four Parts :
Stator : Hydrotris(indazolyl)borate ligand
Rotor : Substituted Cp terminated by ferrocenyls
Insulator : trans Pt(II) complex
Joint : Ruthenium atom
L
Pt
Pt
PtPt
Pt
LL
L
L
LL
L
L
LFe
Fe
Fe Fe
Fe
NN
NN
NN
BH
RuL = PEt3
COOEt COOEtCOOEt
6-3,00E-06
-2,00E-06
-1,00E-06
0,00E+00
1,00E-06
2,00E-06
3,00E-06
4,00E-06
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
E (V/ECS)
i(A
)
-3,00E-06
-2,00E-06
-1,00E-06
0,00E+00
1,00E-06
2,00E-06
3,00E-06
4,00E-06
5,00E-06
6,00E-06
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
E (V/ECS)
i(A
)
INSULATING ROLE OF PLATINUM
- Electrochemical Study
Fe Fe
1
Pt
PEt3
PEt3Fe Fe
2
E1/2(1)
(V/CSE)
E1/2(2)
(V/CSE)
E1/2
(mV)
1 0,58 0,68 ~ 100
2 0,32 0,40 ~ 80
1
2
7
INSULATING ROLE OF PLATINUM
- Spectoelectrochemical Study
1
2
MM
ab RV
2/12/1maxmax
21005.2
Hush formula:
1 : Vab = 0,036 eV
2 : Vab = 0,025 eV
Parametre of electronic coupling :
8
INSULATING ROLE OF PLATINUM
DFT (BP86 / 6-31 G**) Geometry optimisation
Fe
FePt
PMe3
PMe3Fe
Fe
9
INSULATING ROLE OF PLATINUM
dxy dx2-y2
dz2
dxz dyz
HOMO (u)
LUMO (g)
2Vab
E
Fe --- Fe Ligand
Vab calculation: dimer splitting method
Fe Fex
y
dx2-y2 dxy
Overlaping between 3d orbital of Fe and the bridging ligand
E3d(Fe) E(u) E(g) E (eV) Vab (eV)
1 -10,500 -10,767 -10,903 0,136 0,068
1 -11,000 -11,117 -11,272 0,155 0,077
1 -11,500 -11,390 -11,649 0,259 0,129
2 -10,500 -10,849 -10,813 0,036 0,018
2 -11,000 -11,231 -11,186 0,045 0,022
2 -11,500 -11,522 -11,612 0,090 0,045
Energies of the orbitals and Vab of 1 and 2
~ Vab/3 with Pt
10
RETROSYNTHETHIC ANALYSIS
Ru
Fe
FeFe
Fe FeN
NN
NBH
NN
PtPt
Pt Pt
PtL
L
L
L
L
L
L
L
LL
L=PEt3 PtCl
PEt3
PEt3 Fe
B
N
N
N
N
N
N
H
H
H
H
H H
Ru
Br
N
N
N
N
B
H
N
N
Br Br
BrBr Ru+
Pt
PEt3
PEt3 Fe
+
11
SYNTHESIS OF THE RUTHENIUM CENTER
Br
Br
Br
BrBr
Br HTIPS
TIPS
TIPS
TIPS TIPS
TIPSA
CuI, Pd(PPh3)4Et2NH, THF
BuLi
NBS THF
80 %
BrTIPS
TIPS
TIPS
TIPS TIPS
55 %
Ru
OCCO
Br
Ru
B
N
NN
N
N
N
H
Ru3CO12 KTIBTIPS
TIPS
TIPS
TIPS TIPS
TIPS
TIPS
TIPS
TIPS TIPS71 % N
N
N
N
B
H
N
N
Ru
H
H
H H
H
TBAF
Toluene THF
16 %
THF
61 %
12
SYNTHESIS OF A MODEL MOTOR
Ru
Fe
FeFe
Fe FeN
NN
NBH
NN
PtPt
Pt Pt
PtPEt3
Et3P
Et3P
PEt3
PEt3
Et3P
Et3P
PEt3
PEt3Et3P
N
N
N
N
B
H
N
N
Ru
Fe
Pt
PEt3
PEt3
Cl
H
H
H H
HCuI, Et2NH, THF
41 %
Fe
PtCl2(PEt3)2
CHCl3, NHEt286 %
Pt Cl
PEt3
PEt3Fe
Pt fragment synthesis:
Connection
13
CARACTERISATIONS
1.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.58.08.0
a-e b c d
o m
Cp
Cp subs Cp subsCH2
CH3
1H RMN (CD2Cl2) 500 MHz
31P RMN
2244668810101212141416161818202022222424
195Pt {31P} RMN
L
Pt
Pt
PtPt
Pt
LL
L
L
LL
L
L
LFe
Fe
Fe Fe
Fe
NN
NN
NN
BH
RuL = PEt3a
b
cd
e
o m
JPt-P(trans) = 2374 Hz
14
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Fe(II) / Fe(III)
5 e-
Ru(II) / Ru(III)
1 e-
CARACTERISATIONS
Electrochemistry : CV : CH2Cl2, nBu4PF6 0.1 M, 100 mV.s-1
E1/2 (V/SCE) Fe Ru
0.31 0.60
0.52 0.82NN
NN
NN
BH
Ru
Fe
Fe
FeFe
Fe
L
Pt
Pt
PtPt
Pt
LL
L
L
LL
L
L
LFe
Fe
Fe Fe
Fe
NN
NN
NN
BH
RuL = PEt3a
b
cd
e
o m
15
FUNCTIONALISED STATOR FOR OXIDE SURFACES
COOH
NH2
COOEt
NH2SOCl2, EtOH
98%
COOEt
NHN1) Ac2O, AcOK
isoamylnitriteToluene
2) HCl
64%
KBH4, 180°C
72%
NN
B
EtOOC
NN
COOEt
NN
COOEt
H
K
Ligand synthesis
Model Ru complex
Ru
N NN
KTp4BoCO2Et
NN
NN
NN
BH
Ru
COOEt COOEtCOOEt
MeMe
Me
PF6
CH3CN, DMF
16
FIRST MOLECULAR MOTOR
TIPS
TIPS
TIPSTIPS
TIPS
Ru
OCCO Br N
N
NN
NN
BH
Ru
TIPS
TIPS
TIPSTIPS
TIPS
NN
NN
NN
BH
Ru
H
H
HH
H
KTp4BoCO2Et
ACN, DMFMW
TBAF, THF 5% H2O
COOEt COOEtCOOEt COOEt COOEt
COOEt
17%54%
L
Pt
Pt
PtPt
Pt
LL
L
L
LL
L
L
LFe
Fe
Fe Fe
Fe
L = PEt3NN
NN
NN
BH
Ru
COOEt COOEtCOOEt
Pt ClPEt3
PEt3Fe
CuI, Et2NH
35 %
17
PERSPECTIVES
18
AKNOWLEGMENTS
Groupe NanoSciences (CEMES)– Alexandre Carella– Stéphanie Sistach– Gwénaël Rapenne– Jean Pierre Launay– Christine Viala
LCC– Christine Lepetit
Frontiers Network
19
ATP SYNTHASE
A biological rotary motor :
J. E. Walker, Angew. Chem. Int. Ed., 1998, 37, 2308
The rotation of F1 is controled by the proton gradient through the membrane
20
SYNTHESIS OF THE ORGANOMETALLIC CORE
KTIB
Ru
OC COBr
Br
Br
Br
BrBr
Br
Br
Br
BrBr
BrRu
Br
Br
BrBr
Br
B
NN
NN
NN
H
Br2
98%
Ru3CO12
78% 30%
KTIB
B
NN
NN
NN
H
NN
H
KBH4, 220°C
80%
K
21
Fe
PtCl2(PEt3)2
CHCl3, NHEt286 %
Pt Cl
PEt3
PEt3Fe
Pt
PEt3
PEt3FeCuI, Et2NH
91 %
HHH
FIRST STRATEGY
Ru
Fe
FeFe
Fe FeN
NN
NBH
NN
PtPt
Pt Pt
PtL
L
L
L
L
L
L
L
LL
Br
N
N
N
N
B
H
N
N
Br Br
BrBr Ru Pd(PPh3)4Fe
Pt
PEt3
PEt3
ZnCl
+
Pt fragment synthesis:
Connection:
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