- PDF ΔΩΡΕΑΝ Λήψη

S Me 2 OC S Me S S

Me2OC S S COMe 2 Step 1 Step 5 b S COMe 2 Step 1' Me 2 OC S hv Base hv S S S S (3'S)-(M)-1 (3'S)-(P)-1' (3'R)-(P)-1 (3'R)-(M)-1' Clockwise Anticlockwise rotation Epimerization rotation Step 4 Step 2 changes the direction of rotation Step 4' Step 2' Me 2 OC S hv S COMe 2 Base S COMe 2 hv Me 2 OC S Step 3 Step 5' Step 3' S S S S (3'S)-(P)-1' (3'S)-(M)-1 (3'R)-(M)-1' (3'R)-(P)-1

a b c d e f a b g h

d c b a l f e g j m n k h i o 50 Å Herringbone 5 Å

0 63 90 123 166 180 195 228 256 270 318 360 a b 20 Å 10 Å

'-. % &, *',,!'& 3 $B6 $$ $ %'$6 -$ -&!)- # $ - S >,- $ *',,!'& - %', -* 6$,*!)- & '&,!'& +! 6* &, + ('!&, +? $', "#.-34-'0 #6.*'/3#0 2&>-0'/3#+#,2!#1-1#04 2'-,1 #6.>0'+#,2 *#1Q *# 1712=+# >23"'> >2>.*!> ",1 *#! "0# "Z3, +-"=*# "#.&71'/3#!* 11'/3# +'1 3.-',2. 0 123+',x~T Chiral tip R % & Chiral tip R % & & & 0.38 V/5 % &$ pa 0.38 V/5 pa % &$ Rotor S Rotor R R o. of occurrences Directionality 5.0 $,"( 0 ("+ / ± 0.3% Rate 30 ± 10 Hz % &$ o. of occurrences 100 90 80 70 60 50 40 30 20 10 0 " # & " # b 180 S & 180 Directionality 0.2 ("* 0 ("+ / ± 0.3% Rate 90 ± 10 Hz % &$ 180 120 60 60 120 Rotational hop %'& angle ( ) 180 c v=1 v=1 0.38 Energy (ev) % & Energy (ev) % & 0.38 ) 120 60 60 120 Rotational hop angle ( ) %'& 100 90 80 70 60 50 40 30 20 10 0 0.01 v=0 0 0.01 v=0 0 180 120 60 0 60 120 180 Rotor orientation ( ) %'& 180 120 60 0 60 120 Rotor orientation ( ) %'& 180! -* RX > H % + -0 6& &,!'%5* +, - - & *',,!'& +-* -GRRRH? ''% & -, 3 - > (( * & - 3 $B6,, +,,!)-? H (*6+ &,,!'&+ * (!)- + + 0!,,!'&+ 6$,*!)- + - G H, - G H@ - +-* -GRRRH? H!+,' * %% $!+,*! -,!'& +,,!+,!)- + & $ + *',,!'& + -0 6& &,!'%5* +? H *'!$+ 6& * 6,!)- + (*'('+6+ + 6,,+ '& % &, -0, 0!,6+ + -0 6& &,!'%5* + & *',,!'& G* +(,!. % &,, H! &, -& + &+ (*6 6* &,! $ *',,!'&? TQ

(R) C 6 H 13 C 6 H 13 (R) (S) (S) C 6 H 13 C 6 H 13

a b c d 100 c 100 10 excitation steps 80 80 60 60 Final position 40 40 10-step 20 20 trajectory 0 0 Starting position 300 500 700 900 40 120 200 280 e Voltage (mv) Voltage (mv) 6 nm Movement success (%) Helix inversion success (%)

Meso-isomer Meso-isomer (R,R-R,R) isomer correct landing wrong landing

Fe Fe Fe Fe Ru B H Fe O O Ru B H EtS SEt SEt EtS

Ru B O O H S

H 2 Ru 3 (CO) 12 98 % 78 % Ru OC OC

H 2 SOCl 2, EtOH H 2 1) Ac 2 O, KOAc isopentyl nitrite 2) HCl H 98 % 68 % O OH O O O O LiAlH 4, THF H 1) MsCl, Et 3, AcOEt 2) EtSH, KOH, EtOH H 93 % 11 % OH S

H H, AcOH H EtSH, DBU, THF 70 % H 86 % OH S EtSH, ah, THF 56 %

H PhPhOH, Base chauffage H O

O H Ac 2 O, THF PhPhOH, ah, TBAI, THF O O O

O H H 3 7M, MeOH O 96 % O H 3 7M, MeOH 97 %

CH 2 benzyl. 10 3 2 1 7 4 6 5 O 12 13 14 16 15 O 9 10 11 3 2 1 7 4 6 5 O 12 13 14 16 15 CH 2 benzyl. 12 O 9 10 11

H SO 2 CH 3 SO 2 CH 3 SO 2 CH 3 OH OSO 2 CH 3 OH Cl

H Et 3 MsOMs SO 2 CH 3 1) EtSH, DBU 2) H +, H 2 O H OH OSO 2 CH 3 S H ah MsOMs SO 2 CH 3 PhPhOH ah SO 2 CH 3 H OH OSO 2 CH 3 OPhPh OPhPh

K H KBH 4, DMF O B H H O 58% O

B K H H B K O H S O H O O S

B H SiEt 3 DME H B F 3 CF 2 C F F F F DME H, ah F 3 CF 2 C a F 3 CF 2 C F F B F F F F H F F CF 2 CF 3 F F F -SiEt 3

O 2 O 2 O 2 HOOC HOOC COOH O 2 COOH O 2 O 2 O 2 O 2 HOOC COOH COOH HOOC

R' Fe Fe R R R = Fe Ru Fe R Ru R SEt B H SEt EtS SEt B H SEt EtS R' =,,

H KBH 4 K B H S 55 % S S S

O O Fe(CO) 5 O O 31% 79%

O B O O n-buli OH OH, MgSO 4 HO B OH O B O 1) n-buli 2) B(OiPr) 3

HO B OH Pd(PPh 3 ) 4 31% HO B OH Pd(PPh 3 ) 4 55%

CH 3 CH 2 MgCl, OH n-buli, I iprmgcl Cl Mg H I H 2 O H H I (HO)MgCl

HO B OH Pd(PPh 3 ) 4 38% HO B OH Pd(PPh 3 ) 4 26%

MgCl iprmgcl H OH Li nbuli H OH

[Pd] Pd(PPh 3 ) 4, B(OH) 2

O Pd(PPh 3 ) 4, B(OH) 2 O

O Pd(PPh 3 ) 4, B(OH) 2 O 64% 1) nbuli 2) OH 54%

OH H, AcOH 65%

Ru 3 CO 12 OC OC Ru

OC OC Ru Ru B H SEt SEt EtS

H H H H H H Porph Pc Pc

C R 1 C R 2 tétramérisation cyclique M III (acac) 3, DBU [M III (Pc) 2 ] [M III 2(Pc) 3 ] M III (acac) 3, solvant (haute T ) Li 2 Pc ou H 2 Pc

C R 1 C R' 1 C R 2 C R' 2 double tétramérisation cyclique M III (acac) 3 [M III (Pc)(acac)] tétramérisation cyclique C R' 1 [M III (Pc)(Pc')] tétramérisation cyclique C R 1 [M III (Pc')(acac)] C DBU R' 2 M III (acac) 3, DBU C DBU R 2 H 2 Pc H 2 Pc' ou ou Li 2 Pc Li 2 Pc'

H 2 Porph [M III (Porph)(acac)] Li 2 Pc tétramérisation cyclique H 2 Porph [M III (acac) 3 ] [M III (Porph)(Pc)] C R 1 [M III (Porph)(acac)] M III (acac) 3 C R 2 DBU [M III (acac)(pc)] solvant (haute T ) Li 2 Pc H 2 Porph

STM tip-induced electric field

C O n Bu H 21 C 10 S Eu S C 10 H 21 H S 21 C 10 S C 10 H 21 H 21 C 10 S S C 10 H 21 S S H C 10 H 21 21 C 10 A D

C O n Bu H 21 C 10 S Eu S C 10 H 21 H 21 C 10 S S C 10 H 21 H 21 C 10 S S C 10 H 21 S H 21 C 10 S C 10 H 21 C C C Eu O O SC 10 H 21 SC 10 H 21 O n Bu H H C C H

C H H C C H H O n Bu n BuO H H O n Bu A 2 C 2 ABC 2 B 2 C 2 H O H O 1), H 40 eq. 2) O TFA 3) H H H H C TFA DDQ O n Bu H C H O n Bu

2,0 4,2 2,0 2,1 2,2 2,1 2,1 2,0 2,1 2,1 2,4 10,1 3,7 6,0 0,7 1,3 ppm 10,368 9,471 9,462 9,452 9,443 9,155 9,145 9,008 8,999 8,412 8,408 8,400 8,396 8,184 8,179 8,171 8,167 8,145 8,142 8,133 8,129 7,370 7,365 7,357 7,353 6,744 5,333 5,322 5,320 5,318 4,311 4,298 4,285 2,021 2,008 2,002 1,993 1,990 1,977 1,964 1,728 1,713 1,698 1,687 1,683 1,668 1,653 1,142 1,127 1,112 0,086 H C O n Bu 1 2 5 6 1617 20 3 4 7 H 15 18 19 8 14 10 12 9 11 13 ppm 10 9 8 7 6 5 4 3 2 1 0-1 -2-3

1) K 2 CO 3 2) C C C S SH C S

H Eu(acac) 3, nh 2 O C C O n Bu H Eu O n Bu O O

C O n Bu C O n Bu Eu O O DBU C SC 10 H 21 C SC 10 H 21 H 21 C 10 S Eu S C 10 H 21 H S 21 C 10 S C 10 H 21 H 21 C 10 S S C 10 H 21 S S H 21 C 10 C 10 H 21

δ δ m o Ru OC OC

δ δ 2 3 4 6 5 O O δ 7 H 2

δ δ 1 2 3 7 4 6 5 O H O

δ 1 2 3 7 4 6 5 H OH 3 2 1 4 6 5 H S 7

δ 1 2 3 7 4 6 5 H 3 2 1 H 7 4 6 5 12 13 14 16 15 O 9 10 11

δ δ 1 2 3 7 4 6 5 O 3 2 1 7 4 6 5 O

δ δ δ δ 1 2 3 7 4 6 5 O O 9 10 11 12 13 14 16 15

δ 1 2 3 7 4 6 5 14 15 12 13 16 11 O 9 10 O

16 1 2 3 7 4 6 5 14 15 12 13 H 11 9 10 O

1 2 3 7 4 6 5 SO 2 CH 3 OSO 2 CH 3

δ 1 2 3 7 4 6 5 SO 2 CH 3 O 16 9 12 13 10 11 14 15 δ δ

K B δ 16 15 14 12 13 1 2 3 O 4 9 11 O 10 5 6 H H SEt K B H SEt 7 6 EtS 1 2 5 3 4

δ δ δ 1 2 4 3 5 O 6 δ

O δ 2 1 O B O

δ 6 5 2 7 4 3 δ δ 1 10 9 6 11 8 7 4 3 1 5 2

δ 6 5 2 1 7 4 3 δ δ

10 9 6 5 2 1 11 8 7 4 3 δ δ OH

O 6 5 2 1 6' 5' δ 2' 1'

O o m o' m' λε δ δ

OH λε δ

1 2 5 6 λε δ

δ OC OC Ru

C O n Bu H 21 C 10 H S 21 C 10 S Eu S C 10 H 21 S C 10 H 21 H 21 C 10 S S C 10 H 21 S S H 21 C 10 C 10 H 21 λε

H C O n Bu 1 2 5 6 1617 20 3 4 7 H 15 18 19 8 14 10 12 9 11 13 δ

δ λε - - C SC 10 H 21 C 2 4 6 1 3 5 SC 10 H 21