362nd WEH SEMINAR Advances and Prospects in Molecular MagnetismBad Honnef, 11 - 16 November 2005
Andrea CORNIA INSTM & Department of Chemistry, University of Modena & Reggio Emilia (Italy)
Organizing Single-Molecule Magnetson Surfaces
-3 -2 -1 0 1 2 3
-20
-10
0
10
20
Ma
gn
eti
za
tio
n (
µµ µµB)
Magnetic field (T)
2.1K
362nd WEH SEMINAR Advances and Prospects in Molecular MagnetismBad Honnef, 11 - 16 November 2005
C. Zanardi, L. ZobbiINSTM & Dept. of Chemistry, Univ. of Modena & Reggio Emilia, Italy
A. Caneschi, D. Gatteschi,M. Mannini, R. SessoliINSTM & Dept. of Chemistry, Univ. of Florence, Italy
B. Jan Ravoo, N.D. Reinhoudt, E.A. SpeetsLaboratory of Supramolecular Chemistryand Technology, MESA+ Institute forNanotechnology, University of Twente, The Netherlands
D. BarrecaISTM-CNR & INSTM, Departmentof Chemistry, University of Padova, Italy
E. TondelloINSTM & Department of Chemistry, University of Padova,
Italy
Outline1. The chemistry of Mn12 Single-Molecule Magnets
2. 2D domains of Single-Molecule Magnets
2.1 Motivation2.2 By surface pre-functionalization2.3 By direct deposition2.4 By Micro-Contact Printing
3. From densely-packed to isolated clusters
4. Conclusions & Perspectives
362nd WEH SEMINAR Advances and Prospects in Molecular MagnetismBad Honnef, 11 - 16 November 2005
Manganese(IV) (s = 3/2)
Manganese(III) (s = 2)
Oxygen
Carbon
Hydrogen
[Mn12O12(OAc)16(H2O)4]·2AcOH·4H2O
T. Lis, Acta Crystallogr. B. 1980, 36, 2042
S = 10 (Giant Spin)
Mn(OAc)2•4H2O + KMnO4
[Mn12O12(OAc)16(H2O)4]·2AcOH·4H2O (80%)
60% v/v AcOH/H2O
Ligand exchange
[Mn12O12(OAc)16(H2O)4] + xRCO2H [Mn12O12(OAc)16-x(O2CR)x(H2O)4] + xAcOH
toluene/AcOH azeotrope 72/28%, bp 100.6 oC (vs. 110.7 / 118.1oC)
[Mn12] + PPh4I PPh4[Mn12] +1/2I2
Redox
[Mn12O12]+ → [Mn12O12] → [Mn12O12]
- → [Mn12O12]2-→ [Mn12O12]
3-
Reactivity of [Mn12O12(OAc)16(H2O)4]
M. Soler, et al. Inorg.Chem. 2001,40,4902; H. J. Eppley, et al. J.Am.Chem.Soc. 1995,117,301
M. Pacchioni, et al. Chem. Commun. 2004, 2604.
[Mn12O12(OAc)16(H2O)4] + 16PhCO2H [Mn12O12(O2CPh)16(H2O)4] + 16AcOHtoluene
[Mn12O12(O2CPh)8(L)4(H2O)4] + 8PhCO2H[Mn12O12(O2CPh)16(H2O)4] + 4H2LCH2Cl2/hex
H2L[Mn12O12(O2CPh)8(L)4(H2O)4]
Reactivity of [Mn12O12(OAc)16(H2O)4]
2D Domains of Single-Molecule Magnets
Motivation
New Physics and Applications
� magnetic behaviour of “isolated” single-molecule magnets
� role of the environment
� writing and reading magnetic information on a single molecule
� ultra-high density information storage (10 Tbit/cm2)
•Langmuir-Blodgett films withbehenic acid (C21) M. Clemente-Leon et al., Angew. Chem. IE 1998, 37, 2842
•Photolithographically fabricated patterns on Si/SiO2K. Kim et al., Appl. Phys. Lett. 2004, 85, 3872
•Stamp–assisted deposition on Si/SiO2M. Cavallini et al., Nano Lett. 2003, 3, 1527
•Dispersions in polymersD. Ruiz–Molina et al., Adv. Mater. 2003, 15, 42 M. Cavallini et al., Angew. Chem. Int. Ed. 2005, 44, 888
solvent vapors
2D Domains of Single-Molecule Magnets
2D Domains of Single-Molecule Magnets
� Stable (sub)monolayers
� Covalently bound
� Oriented
� On conducting substrates
STMtip
Au
Pre-functionalized surfaces + Native clusters
Native surfaces + Pre-functionalized clusters
Pre-functionalized surfaces + Pre-functionalized clusters
Grafting on pre-functionalized Si(100) surfacesG. G. Condorelli et al.,Angew. Chem. Int. Ed. 2004, 43, 4081 [Mn12O12(O2CCH3)16(H2O)4]
B. Fleury et al.,Chem. Commun. 2005, 2020 [Mn12O12(O2CCHCl2)8(O2CCH2Bu
t)8(H2O)3]
AFM400 x 400 µm
AFM70 x 70 µm
2D Domains of Single-Molecule Magnets
J. S. Steckel et al., Nano Lett. 2004, 4, 399[Mn12O12(O2CCH3)16(H2O)4]
A. Nait Abdi et al., Adv. Mater. 2005, 17, 1612[Mn12O12(O2C
tBu)16(H2O)4]
Grafting on pre-functionalized Au(111) surfaces
Quartz Crystal Microbalance
2D Domains of Single-Molecule Magnets
16-(acetylthio)hexadecanoic acid
Mn12-bindinggroup
Au-bindinggroup
spacer
[Mn12O12(OAc)16(H2O)4] + 16RCO2H [Mn12O12(O2CR)16(H2O)4] +16AcOH
Direct Deposition on Au(111)
5.0 ×××× 5.6 nm
[Mn12O12(L)16] + H+
MALDI-TOF
[Mn12O12(OAc)n(L)16-n](M’= M-270n)
A. Cornia, et al. Angew. Chem. IE 2003, 42, 1645
16-(acetylthio)hexadecanoic acid
Mn12-bindinggroup
Au-bindinggroup
spacer
[Mn12O12(OAc)16(H2O)4] + 16RCO2H [Mn12O12(O2CR)16(H2O)4] +16AcOH
A. Cornia et al. Angew. Chem. IE 2003, 42, 1645; L. Zobbi, et al. Chem. Commun. 2005, 1640
5.0 ×××× 5.6 nm
K)8(1.55/U
s10)4(4.28
0
=
⋅=−
Bk
τ
AC-Magn. Susc.
A. Cornia, et al. Angew. Chem. IE 2003, 42, 1645
Direct Deposition on Au(111)