frontiers workshop design and synthesis of a molecular motor incorporating insulating fragments...
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![Page 1: Frontiers Workshop Design and Synthesis of a molecular motor incorporating insulating fragments Guillaume Vives PhD Supervisors : Gwénaël Rapenne and Jean-Pierre](https://reader035.vdocuments.site/reader035/viewer/2022062323/5697bfab1a28abf838c9b31c/html5/thumbnails/1.jpg)
Frontiers Workshop
Design and Synthesis of a molecular motor incorporating insulating
fragments
Guillaume Vives
PhD Supervisors : Gwénaël Rapenne and Jean-Pierre Launay
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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
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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
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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 :
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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
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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
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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 :
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8
INSULATING ROLE OF PLATINUM
DFT (BP86 / 6-31 G**) Geometry optimisation
Fe
FePt
PMe3
PMe3Fe
Fe
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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
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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
+
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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 %
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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
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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
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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
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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
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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 %
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17
PERSPECTIVES
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18
AKNOWLEGMENTS
Groupe NanoSciences (CEMES)– Alexandre Carella– Stéphanie Sistach– Gwénaël Rapenne– Jean Pierre Launay– Christine Viala
LCC– Christine Lepetit
Frontiers Network
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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
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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
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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: