Phenol-pyrazole ligands in the design of manganese(III) compounds : synthesis, structural characterization and study of the magnetic
properties
Viciano Chumillas, Marta
Citation
Viciano Chumillas, M. (2009, October 22). Phenol-pyrazole ligands in the design of manganese(III) compounds : synthesis, structural characterization and study of the magnetic properties. Coordination and Bioinorganic Chemistry Group (CBAC), Faculty of Science, Leiden University. Retrieved from https://hdl.handle.net/1887/14201
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Phenol-pyrazole ligands in the design of manganese(III) compounds:
Synthesis, structural characterization and study of the magnetic properties.
PROEFSCHRIFT
Ter verkrijging van
de graad van Doctor aan de Universiteit Leiden,
op gezag van Rector Magnificus professor mr.P.F.van der Heijden, volgens besluit van het College voor Promoties
te verdedigen op donderdag 22 oktober 2009 klokke 16.15 uur.
door
Marta Viciano Chumillas
geboren te Valencia, Spanje in 1980
Promotiecommissie
Promotor Prof. Dr. J. Reedijk Prof. Dr. L. J. de Jongh Co-promotor Dr. S. Tanase Grecea
Overige leden Dr. E. Bouwman (Universiteit Leiden, The Netherlands) Prof. Dr. M. Julve (Universitat de València, Spain) Prof. Dr. M. Drillon (Université Strasbourg, France)
Prof. Dr. J. Brouwer (Universiteit Leiden, The Netherlands)
Prof. Dr. J. M. van Ruitenbeek (Universiteit Leiden, The Netherlands)
This work has been supported financially by the European Networks MAGMANet, Network of Excellence (No. 515767) and QueMolNa (No. MRTN-CT-2003-504880).
Printed by Wöhrmann Print Service, Zutphen , The Netherlands, 2009.
Quan surts per fer el viatge cap a Ítaca, has de pregar que el camí sigui llarg, ple d'aventures, ple de coneixences.
Has de pregar que el camí sigui llarg, que siguin moltes les matinades
que entraràs en un port que els teus ulls ignoraven, i vagis a ciutats per aprendre dels que saben.
Tingues sempre al cor la idea d'Ítaca.
Has d'arribar-hi, és el teu destí, però no forcis gens la travessia.
És preferible que duri molts anys, que siguis vell quan fondegis l'illa,
ric de tot el que hauràs guanyat fent el camí, sense esperar que et doni més riqueses.
Ítaca t'ha donat el bell viatge, sense ella no hauries sortit.
I si la trobes pobra, no és que Ítaca t'hagi enganyat. Savi, com bé t'has fet, sabràs el que volen dir les Ítaques.
(Part of Ítaca, song of L. Llach based on a poem of K. Kavafis)
A mis padres
Contents
List of abbreviations
Chapter 1 Introduction 7
Chapter 2 A family of mononuclear compounds: [Mn(HphpzR)
2X] (R = H, Me, Et, Ph; X
–= Cl
–, Br
–)
37
Chapter 3 Mononuclear compounds as building blocks for the design of
trinuclear manganese(III) compounds with the [Mn
3( P
3-O)(phpzR)
3]
+core
61
Chapter 4 From 1-D to isolated trinuclear compounds: impact of the co-ligand and the carboxylate on the core [Mn
3( P
3-O)(phpzR)
3]
+89
Chapter 5 Manganese(III) compounds of high nuclearity 107 Chapter 6 Coordination versatility of 3(5)-methyl-5(3)-(2-hydroxyphenyl)-
pyrazole with Co(III), Ni(II) and Cu(II) ions
123
Chapter 7 Summary, concluding remarks and perspectives 137 Appendix A HFEPR spectroscopic studies for [Mn(HphpzR)
2X] (X
–= Cl
–, Br
–) as
complementary technique to magnetic susceptibility and specific heat techniques
145
Appendix B Crystallographic information for compounds of Chapter 5 159
Samenvatting 165
Resumen 171
Curriculum vitae 175
List of publications 176
Acknowledgements 177
List of abbreviations
H2phpzH 3(5)-(2-Hydroxophenyl)-pyrazole
H2phpzMe 3(5)-(2-Hydroxophenyl)-5(3)-methylpyrazole H2phpzEt 3(5)-(2-Hydroxophenyl)-5(3)-ethylpyrazole H2phpzPh 3(5)-(2-Hydroxophenyl)-5(3)-phenylpyrazole H2salen N, N’-bis(salicylidene)ethylenediamine DPPH 2,2-Diphenyl-1-picrylhydrazyl radical
IR Infrared Spectroscopy
ESI-MS Electrospray Mass Spectroscopy NMR Nuclear Magnetic Resonance
UV/VIS/NIR Ultraviolet-Visible-Near Infrared
(HF)EPR (High Field or High Frequency) Electron Paramagnetic Resonance
CV Cyclic Voltammetry
SQUID Superconducting Quantum Interference Device
AC Alternating Current
DC Direct Current
PPMS Physical Property Measurement System
TGA ThermoGravimetric Analysis
g Electron gyromagnetic factor (2.002 for a free electron) AN Hyperfine splitting parameter (G)
kB Boltzmann constant, 1.3806580u1023 JK1 (0.69503877 cm1K1) N Avogadro’s number, 6.022u1023 mol1
E(PB) Bohr Magneton, 9.274u1024 JT1 (4.66864374u105 cm1G1) FM Molar magnetic susceptibility (cm3mol1)
B(K) Brillouin function
J Magnetic exchange parameter (cm1)
ZFS Zero-Field Splitting
D, E Zero-Field Splitting parameters, axial and rhombic components (cm1) Cm Magnetic heat capacity (JK1mol1)
Cl Lattice heat capacity (JK1mol1) R Gas constant, 8.314472 JK1mol1
M Magnetization
Sm Entropy (JK1mol1) TD Debye temperature (K) O Molecular field constant T Curie-Weiss temperature
SMM Single-molecule magnet
ST Spin ground state
