SELF ASSEMBLY OF COORDINATION CAGES ON SI(100) SURFACES
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SELF ASSEMBLY OF COORDINATION CAGES ON SI(100) SURFACES G. G. Condorelli 1 , M. Busi 2 , E. Dalcanale 2 , M. Favazza 1 , I. L. Fragalà 1 , M. Laurenti 2 , M. Montalti 3 , A. Motta 1 , L. Prodi 3 Dip. di Scienze Chimiche, Università di Catania and INSTM UdR di Catania Dip. di Chimica Organica e Industriale, Università di Parma , and INSTM UdR di Parma Dip. di Chimica "G. Ciamician", Università di Bologna
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SELF ASSEMBLY OF COORDINATION CAGES ON SI(100) SURFACES. G. G. Condorelli 1 , M. Busi 2 , E. Dalcanale 2 , M. Favazza 1 , I. L. Fragalà 1 , M. Laurenti 2 , M. Montalti 3 , A. Motta 1 , L. Prodi 3 Dip. di Scienze Chimiche, Università di Catania and INSTM UdR di Catania - PowerPoint PPT Presentation
Transcript of SELF ASSEMBLY OF COORDINATION CAGES ON SI(100) SURFACES
SELF ASSEMBLY OF COORDINATION CAGES ON SI(100) SURFACES
G. G. Condorelli1, M. Busi2, E. Dalcanale2, M. Favazza1, I. L. Fragalà1, M. Laurenti2, M. Montalti3, A. Motta1, L. Prodi3
Dip. di Scienze Chimiche, Università di Catania and INSTM UdR di Catania
Dip. di Chimica Organica e Industriale, Università di Parma, and INSTM UdR di Parma
Dip. di Chimica "G. Ciamician", Università di Bologna
Cavitands for Self-assembly
Internal volume 18003Å
M=Pt, PdL=1,3-bis(diphenylphosphino)propane (dppp)X= CF3SO3
- (OTf-)
R
O
R
O O
R
O O O
N
O
R
O
N NN 4 MLX2
NEt3 OO OOO O
N
O O
N NN
R R RR
OOO OOO
N
OO
NN N
RRR R
LM LM ML ML
8+
8X-
Nanotechnologies:Precise control over the formation of nanoscale molecular architectures
Self-assembly is a key technology for the formation of two- and three-dimensional structures.
Appealing points:Thermodynamic controlReversibility
Metal-directed self-assembly of coordinantion cages
OO OOO O
N
O O
N NN
Si Si Si Si Si
Si
H
Si
H
Si
H
Si
H
Si
H
Si
H
OO OOO O
N
O O
N NN
Si Si
H
SiSi Si
H
Si
OOO
OO
O
N
O
O
N
N
N
RR
R
Si Si Si Si Si
R
4 MLX2OO OOO O
N
O O
N NN
Si Si
H
SiSi Si
H
Si
OOO OOO
N
OO
NN N
RRR R
LM LM ML ML
Si Si Si Si Si
8+
8X-
From solution to technological surface (Si(100))
Nanostructured hybrid material covalent bonded to Si:
Stable for long time storage
Possible integration in real device
Reversible inclusion of single molecules with functional properties
A possible route towards nanoreplication
Cavitand grafting on Si(100)
Si 2p XPS spectra: Si 2p XPS spectra: give information on the give information on the quality of the monolayerquality of the monolayer
H HH HH HH H H HH HH H
Si Si Si Si Si
OO O
OO
O
N
OO
N
N
N
OO O
OO
O
N
OO
N
N
N
OO OOO O
N
O O
N NN
OO OOO O
N
O O
N NN
OO OOO O
N
O O
N NN
104 100 96
0.0
0.2
0.4
0.6
0.8
1.0
96100104
0.0
0.2
0.4
0.6
0.8
1.0
BE (eV)
No
rm
ali
zed
In
ten
sity
b)
BE (eV)
Oxidated Si:layer not densely packed
freshly HFetched
pure cavitaddecorated
SiOx
254nm
SiOx
Cavitand grafting on Si(100)
Si 2p XPS spectra: Si 2p XPS spectra: give information on the quality of the monolayergive information on the quality of the monolayer
OO OOO OO
N NN N
O OO OOO OO
N NN N
O
Si Si Si Si SiSi Si Si Si SiSi Si Si Si SiSi Si Si Si Si SiSi Si Si Si Si Si
M= Pt L= dppp
254nm254nm
H HH HH HH H H HH HH H
Si Si Si Si Si Si
H HH HH HH H H HH HH H
Si Si Si Si Si Si
OO
O
OO
OO
N
N
N
N
O
321
8+
8 OTf-
i) ii)
104 100 960.0
0.2
0.4
0.6
0.8
1.0
BE (eV)104 100 96
0.0
0.2
0.4
0.6
0.8
1.0
Nor
mal
ized
In
ten
sity
BE (eV)
mixed cavitaddecorated
freshly HFetched
Not oxidated Si:layer densely packed
o
OO
O
OO
OO
N
N
N
NO
OOO
OO
OO
N
N
N
N
O
ML
ML
LM
LM
O
O
O
8+
8 OTf-
OO OOO OO
N NN N
O OO OOO OO
N NN N
O OO OOO OO
N NN N
O OO OOO OO
N NN N
O
OO OOO OO
N NN N
O
LM LM MLML
O
O
Si Si Si Si Si
OO OOO OO
N NN N
O OO OOO OO
N NN N
O
OO OOO OO
N NN N
O
LM LM MLML
O
O
Si Si Si Si SiSi Si Si Si SiSi Si Si Si Si SiSi Si Si Si Si Si
M= Pt L= dppp
254nm254nm
H HH HH HH H H HH HH H
Si Si Si Si Si Si
H HH HH HH H H HH HH H
Si Si Si Si Si Si
321
8+
8 OTf-
i) ii)
Self-assembly of coordination cages
Self –assembly treatmenton cavitand functionalisedsilicon
Control experiment:Self –assembly treatmenton octene functionalisedsilicon Si Si Si Si Si
o
OO
O
OO
OO
N
N
N
NO
OOO
OO
OO
N
N
N
N
OML
ML
LM
LM
O
O
O
8+
8 OTf-
M= Pt L= dppp
ii) Si Si Si Si Si
Chatacterization techniques
X-ray Photoelectron Spectroscopy (XPS)
Atomic Force Microscopy (AFM)
Fluorescence Spectroscopy
XPS analysisXPS analysis
Atomic %
Si O C N Pt F
39.4 16.0 42.1 1.1 - -
23.6 32.9 41.9 1.2 0.03 0.2
36.3 31.5 31.8 0.1 - -
OO OOO O
N
O O
N NN
R R RR
OOO OOO
N
OO
NN N
RRR R
LM LM ML ML
8+
8X-
R
O
R
O O
R
O O O
N
O
R
O
N NN
Pt 4fOO OOO O
N
O O
N NN
Si Si
H
SiSi Si
H
Si
OOO OOO
N
OO
NN N
RRR R
LPt LPt PtL PtL
Si Si Si Si Si
8+
8X-
500 nm/div
500 nm/div
6,6 nm/div
Line
A
B
Height Profile
AB
37,0 nm43,2 nm
1,9 nm2,1 nm
AFM analysisAFM analysis
AFM on the 20% cavitand decorated substrate
1.8nm
3 nm
Molecular modeling
3,8 nm
3,5 nm
1.8 nm
AFM analysis AFM analysis
500 nm/div
500 nm/div
3,9 nm/div
Line
C
BA
Height Profile
A BC
58,9 nm53,0 nm58,8 nm
3,5 nm3,9 nm 4,0 nm
AFM of the Self-assembled cages on Si
Molecular modeling
AFM analysis AFM analysis
500 nm/div
500 nm/div
3,9 nm/div
Line
C
BA
Height Profile
A BC
58,9 nm53,0 nm58,8 nm
3,5 nm3,9 nm 4,0 nm
AFM of the Self-assembled cages on Si
Cages!
500 nm/div500 nm/div
4,5 nm/div
Height Profile
0,8 nmA
Line
A
AFM of the 1-octene decorated substrate after the same treatment of the self-assembled
cages substrate
No Cages!
Fluorescence analysisFluorescence analysis
Excitation by dedicated UV
laser at 355nm on several
areas (1mm2) give:
•No fluorescence emission for
all investigated areas on the
20% decorated cavitand
substrate.
•Fluorescence emission in
different area for the 20%
decorated cavitand substrate
after the self-assembly
treatment.
•No fluorescence emission for
all the investigated areas for
the 1-ottene decorated
substrate after the self-
assembly treatment.
Emission of self-assembled cages on Si.
Reference of phyisisorbed cages deposited on SiEmission of the 1-ottene decorated substrate after the self-assembly treatment.
UV fluorescence in reflection on surfaces
Excimer band
Conclusion A new route for Si-integrattion of 3D nanosize
coordination cages through the self-assembly
The approach associated to the possibility of introducing specific probes offers the advantages of an easy, error-free characterization of complex 3D structures.
Observation for the first time of fluorescence of a dye covalently linked on a Si(100) surface.
Thank you for your attention
XPS analysisXPS analysis
Relevant atomic ratiosN/C F/Pt N/Pt
Exp. 0.026 - -
Theor. 0.027 - -
Exp. 0.028 6.3 40
Theor. 0.035 6 2
OO OOO OO
N NN N
O OO OOO OO
N NN N
O
Si Si Si Si SiSi Si Si Si SiSi Si Si Si SiSi Si Si Si Si SiSi Si Si Si Si Si
M= Pt L= dppp
254nm254nm
H HH HH HH H H HH HH H
Si Si Si Si Si Si
H HH HH HH H H HH HH H
Si Si Si Si Si Si
321
8+
8 OTf-
i) ii)
OO OOO OO
N NN N
O OO OOO OO
N NN N
O
OO OOO OO
N NN N
O
LM LM MLML
O
O
Si Si Si Si Si
OO OOO OO
N NN N
O OO OOO OO
N NN N
O
OO OOO OO
N NN N
O
LM LM MLML
O
O
Si Si Si Si SiSi Si Si Si SiSi Si Si Si Si SiSi Si Si Si Si Si
M= Pt L= dppp
254nm254nm
H HH HH HH H H HH HH H
Si Si Si Si Si Si
H HH HH HH H H HH HH H
Si Si Si Si Si Si
321
8+
8 OTf-
i) ii)
Calculatedcage formation4%
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