Department of Chemistry
(Chemicum)
from basics
research-based
research
knowledge
to applications
education
in society
in service
Welcome to the Department of Chemistry!
Department Composition (education)
• Laboratory of
Analytical Chemistry
Inorganic Chemistry
Organic Chemistry
Physical Chemistry
Polymer Chemistry
Radiochemistry
• Centre for Chemistry Education
• Chemistry ICT Center (eChemicum)
• Laboratory for Instruction in Swedish
• VERIFIN
Strategic Focuses in Research (2004-2006)
 Green chemistry
 Material and nanochemistry
 Computational and theoretical chemistry
Science teacher education and its
reseach
Green Chemistry is the use of chemistry for pollution
prevention.
More specifically, green chemistry is the design of chemical
products and processes that are more environmentally benign.
MATERIALS CHEMISTRY
.
Spacer, by ALD?
CoSi2
Polysilicon
Application areas
Micro- and optoelectronics
Metal oxide gatedielectric, by ALD?
Source
Si-substrate
Metal gate,
by ALD?
Channel Drain
Space applications
MOSFET
transistor
Nuclear waste purification
Grid filter
for X-ray
detector
Biomaterials
Pharmaceuticals
MAKING OF NANOMATERIALS
.
Templating by porous materials
→ nanowires, nanorods
Templating by fibers → nanotubes
Electrospinning → nanowires, nanotubes
Patterning with SAMs
Nanoparticles
Smart polymers and materials
MAKING OF NANOSTRUCTURES
.
Nanowires, nanorods coated by ALD
Glancing angle evaporation
Patterning with SAMs
Star polymers
Block copolymers
free standing porous alumina
+ oblique evaporation
+ electrodeposition
+ dissolution of alumina
+ ALD
THIN FILM MATERIALS
FOR
.
MICROELECTRONICS
Dielectrics for gate oxides in MOSFETs
Dielectric films for DRAMs and FERAMs
Metal films
Nitride films for barriers
14 nm TiN
In collaboration
with NIST
TiCl4 + Zn + NH3  TiN
in collaboration with Intel
Al2O3 film deposited by ALD
from AlCl3 and Al(OiPr)3.
INORGANIC IX MATERIALS: ”ION SIEVES”
FOR HIGHLY SELECTIVE RADIONUCLIDE
SEPARATIONS
EXAMPLES:
Gold nanoparticles with hydrophilic
and hydrophobic polymer grafts
S
CH3
HOOC
S
S
HOOC
CN
HN
O 55
(Cpa-RAFT-PNIPAM Mn = 6450 PDI = 1.11)
PNIPAM
S
CH3
+
HAuCl4
CN
94
(Cpa-RAFT-PS Mn = 10000 PDI = 1.07)
Au
PS
PNIPAM/PS-MPC
Development of miniaturized analytical devices
• Electrospray devices
– PDMS
– SU-8
6,00E+05
TIC +MRM: 455,2/165,1amu ja 455,2/ 303,4 amu
5,00E+05
intensity, cps
4,00E+05
3,00E+05
2,00E+05
1,00E+05
0,00E+00
0
10
20
30
40
50
60
time, min
• Miniaturized atmospheric pressure chemical
ionization (APCI) and photoionization sources
(APPI)
5e+7
(A)
(B)
(C)
Absolute intensity [cps]
4e+7
OH
3e+7
H
H
2e+7
[M+H]+
H
O
1e+7
0
100
150
200
250
300
m/z
350
400
450
500
Development of miniaturized analytical devices
laser
MS
• Methods based on porous silicon
porous area
– Desorption Ionization On Silicon (DIOS)
– Filtration devices
• SU-8 microchannels for CE
Midazolam
MW: 325
sample
Milestones in noble-gas chemistry
•
•
•
•
First compounds predicted already in 1902!
Pauling 1933: XeF6 and KrF6 should be preparable.
Bartlett 1962: first noble-gas compound, Xe[PtF6].
In matrices: First : KrF2 (Turner and Pimentel, 1963).
Others: XeCl2 (Nelson and Pimentel, 1967); ClXeF
(Bondybey, 1971).
• Strong interactions in matrices: Cr(CO)5---Rg (Perutz and
Turner, 1975); Rg---BeO (Thompson and Andrews, 1994).
• XeAuF (Cooke and Gerry, 2004).
• HRgY Pettersson et al., 1995-)
HXeI
2.5
2.0
1.5
HI
1.0
0.5
XeH 2
absorbance
annealed to 45 K
C
B
0.0
A
2300
2200
initial sample
HI/Xe, 1:1000
2100 1300
1250
1200
-1
wavenumber (cm )
1150
1100
photolyzed
Noble gas hydrides
Ar
HArF
Kr
HKrCl
HKrF
HKrCN
HKrCCH
HKrC4H
Xe
HXeH
HXeI
HXeBr
HXeCl
HXeCN
HXeNC
HXeOH
HXeO
HXeSH
HXeNCO
HXeCCH
HXeCCXeH
HXeCC
HXeC4H
18
3.1 Å
1.68 Å
H
Xe
+0.129
+0.347
I
-0.476
MP2/43333/433111/41111(Xe, I)/6-311++G(3d,3p) (H)
Van der Waals -distances:
3.8 Å
H
Experimental:
4.3 Å
Xe
 H-Xe  1193cm
I
-1
 (H-Xe)  2200cm
-1
(HNg)+ + Y-
Avoided crossing
H + Ng + Y
H-Ng-Y
HNgY molecules correlate with neutral atomic asymptote
F-Ar str.
HF / 40Ar
HF / 36Ar
1980
0.0
1960
690
D-Ar str.
0.1
1970
680
440
430
F-Ar str.
-0.1
Absorbance
H-Ar-F bend.
H-Ar str.
0.0
D-Ar-F bend.
Absorbance
0.1
DF / 40Ar
1480
1470
1460
1450 520
510
440
430
-1
Wavenumber (cm )
Effect of isotopic substitution on the fundamentals of HArF
132.9
196.9
Predicted organo-Ng-molecules
• Numerous Xe-containing organic molecules
are known, normally containing F.
Examples:
• R2Xe, where R = C6F5 or 2,4,6-C6H2F3
• [CF3CCXe][BF4]
• So far, no organic Ar compounds known.
• Non-halogen containing organic molecules
predicted in 2002:
HXeC6H5
HXeCCH
HXeOC6H5
Lundell et al. J. Phys.Chem. A 106 (2002) 11950.
HXeCCXeH
Predicted organo-Ng-molecules
• The MP2/LJ18/6311++G(2d,2p) calculated
structure and Mulliken
charges of HCOOXeH
• Works for larger acids,
glycine, alanine and
valine.
• J. Lundell et al.,
Computers&Chemistry, 24
(2000) 325-330.
Xe
H
Acetylenic systems
Electron affinity:
C2H
2.956
C4H
3.558
C6H
3.809
C8H
3.996
• Electron affinity of C2nH
radicals localized at the C end.
•
HNgC6H and HNgC8Hmolecules expected to be more
stable than HNgC4H and
HNgC2H
•
First halogen-free organic Xe
compounds.
•
First organic Kr compounds.
•
Challenge: Organic Arcompound!
Bond lengths
MP2/LJ18(Xe)/6-311++G(2d,2p) level
(Kr)
(Xe)
1.60
1.75
2.25
1.23
2.32
1.23
1.06
1.06
(Kr)
1.58
2.26
1.24
1.37
(Xe)
1.74
2.33
1.24
1.37
1.22
1.22
1.06
1.06
Recent computational predictions
• H-Xe-CC-H
• H-Xe-CC-Xe-H
• H-Xe-CC-Xe- CC-Xe-C  C-Xe-...-H
• E. C. Brown, A. Cohen and B. Gerber, JCP, 122 (2005) 171101.
• F-Kr-CC-H
• F-Kr-SiF3
• S. Yockel, A. Garg, A. Wilson, CPL., 411(2005)91.
Applications?
• Very high energy compounds, could form
solids!
• Specific activation of functional groups:
”Xe-catalysis”.
• Function of Xe in aenesthesia
• Solving the ”missing Xe-problem”