MolecularToys

AdamM.Azman
19March2008

Platonic Solids(theblocks)
Solids (the blocks)
Exactly5
l

Plato
Platotheorizedtheclassicalelementswere
theorized the classical elements were
constructedfromtheplatonicsolids
Octahedrane andicosahedrane areimpossible
hydrocarbons
Tetrahedrane onlypossibleifsubstituted
and dodecahedrane sucessfully
Cubane anddodecahedrane
synthesized

Blocks Cubane

Fi
Firstsynthesizedin1964byEaton
h i d i 1964 b E
Highestdensityofallhydrocarbons(1.29gmL
g
y
y
(
g 1)

O
HO
O

Eaton,P.E.;Cole,T.W.J.Am.Chem.Soc. 1964,86,962964.
Eaton,P.E.;Cole,T.W.J.Am.Chem.Soc. 1964,86,31573158.

O
Br

Blocks Dodecahedrane

Syntheticeffortsbeganin1964(Woodward)
Synthetic efforts began in 1964 (Woodward)
Firsttotalsynthesisin1982byPaquette

1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.

Blocks Dodecahedrane
11

10

O
I

11

10

Zn-Cu
MeOH
9

80%
4 steps

CO2Me
CO2Me

R
4

O
R

H2O2

10

CO2Me
CO2Me

11
7

100%

2) H+
77%

R
R

P2O5
O

1) H2, Pd-C
R

MeSO3H
83%

SPh2

1)

O R

2) NaBH4

O
O

HCl
O

12 of 20 stereocenters
Ester topology to direct all further reagents

MeOH

OMe

Cl
O

Cl

1) Li, NH3
2) PhOCH2Cl
48%, 2 steps

PhOCH2

OMe

OMe

1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.

Blocks Dodecahedrane

1)Paquette,L.A.;Balogh,D.W.J.Am.Chem.Soc.,1982,104,774783.2)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.J.
Am.Chem.Soc.,1982,104,45024503.3)Ternansky,R.J.;Balogh,D.W.;Paquette,L.A.J.Am.Chem.Soc.,1982,104,4503
4504.4)Paquette,L.A.;Ternansky,R.J.;Balogh,D.W.;Kentgen,G.J.Am.Chem.Soc.,1983,105,54465450.

Dolls NanoPutians
NamedafterLilliputiansinJonathanSwifts
GulliversTravels
ll

l
2nmtallanthropomorphicmolecules
p
p
0.006ng =1.105x1014 mol=6.6x109 molecules
=currentworldpopulation

t
ld
l ti
O

NanoKid

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

Dolls NanoPutians

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

Dolls NanoPutians

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

10

Dolls NanoPutians

H
O

O
PdCl2(PPh3)2, CuI
NEt3, THF
85%

I
A
B

NanoKid

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

11

Dolls NanoPutians
O

excess diol
wave, 1-16 min
9-94%

NanoMonarch
87%

NanoPilgrim
25%

NanoAthlete
91%

NanoTexan
24%

NanoGreenBeret
85%

NanoScholar
90%

NanoJester
94%

NanoBaker
84%

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

NanoChef
9%

12

Dolls NanoPutians
O

Au surface

HO

O
O

O
O

O
O

O
O

O
O

Chanteau,S.H.;Ruths,T.;Tour,J.M.J.Chem.Ed.,2003,80,395400.
Chanteau,S.H.;Tour,J.M.J.Org.Chem.,2003,68,87508766.

OH

13

Dolls NanoPutians

14

Racecar Nanocar
Actuallyshowntomovebyrolling notsticksliporsliding
Approximately3x4nm

Shirai,Y.;Osgood,A.J.;Zhao,Y.;Kelly,K.F.;Tour,J.M.Nano.Lett.,2005,5,23302334.

15

Elevator
C
Ca.2.5nmheightx3.5nmdiameter
25
h i h 35
di
Distancebetweenfloors=0.7nm
Movementfromuppertolowerfloor
cangenerate200pN
t 200 N
Designedbasedona[2]rotaxane

Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.

16

Elevator

Stimulus B

Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.

17

Elevator

Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.

18

Elevator

Badji,J.D.;Balzani,V.;Credi,A.;Silvi,S.;Stoddart,J.F.Science,2004,303,18451849.
Badji,J.D.;Ronconi,C.M.;Stoddart,J.F.;Balzani,V.;Silvi,S.;Credi,A.J.Am.Chem.Soc.,2006,128,14891499.

Elevator
Othermolecularmachinesinclude

Motors
Switches
Shuttles
Turnstiles
Gears
Bearings
Gyroscopes

Futureisinincorporatingseveralmolecular
p
g
machinesintoafunctionalmacromolecular
machines
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