1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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Figure 5-5. ORTEP depiction of V-4 showing three-fold disordered tetrachlorogallate anion. Ellipsoids are 50%, H atoms assigned isotropically............................................................................................................146 Figure 5-6. Ball and stick X-ray structure of V-6. Hydrogen atoms have been removed...........................147 Figure 5-7. EPR spectrum (above) and simulation (below) of V-1.............................................................149 Figure 5-8. SOMO of V-1. Calculated using G03W, B3LYP, 6311G(d,p)................................................150 Scheme 5-4. The reaction sequences of o-naphthaquinone to obtain V-11, V-12 and V-13......................155 Figure 5-9. The infrared tramsmission spectrum of the starting material 1,2-naphthoquinone.................157 Figure 5-10. Infrared transmission spectrum of V-11.................................................................................157 Figure 5-11. Infrared transmission spectrum of V-12.................................................................................159 Figure 5-12. Infrared transmission spectrum of V-13.................................................................................159 Figure 5-13. 1 H NMR of V-11 at 300 MHz in DMSO-d 6 ..........................................................................160 Figure 5-14. 1 H NMR spectrum of V-12 at 300 MHz in DMSO-d 6 ............................................................161 Figure 5-15. Possible oxidation states for V-9...........................................................................................163 Scheme 5-5. The reaction sequence of o-naphthaquinone to obtain V-15 and V-16..................................166 Figure 5-16. The infrared transmission spectrum of V-15.........................................................................167 Figure 5-17. The infrared transmission spectrum of V-16.........................................................................168 Figure 5-18. 1 H NMR spectrum of V-15 at 300 MHz in DMSO-d 6 ...........................................................169 Figure 5-19. 1 H NMR spectrum of V-16 at 300 MH in DMSO-d 6 ............................................................171 Figure 5-20. Unit cell of V-15 showing the co-crystallized dioxane molecules as space-fill with the dimerized molecule as wire-frame, illustrating the channels. Hydrogen atoms have been omitted............172 Figure 5-21. ORTEP depiction of V-15 with 50% probability ellipsoids. Hydrogen atoms and dioxane molecules have been omitted........................................................................................................................173 Figure 5-22. Possible oxidation states of V-17...........................................................................................175 xiv
GLOSSARY OF ABBREVIATIONS ° Degrees Å ADP a N AFM β B3LYP bpy bpym n Bu χ Angstrom Atomic Displacement Parameter EPR nuclear coupling constant Antiferromagnetic Bohr magneton Becke, three parameter, Lee-Yang-Parr 2,2′-bipyridine 2,2′-bipyrimidine Butyl Magnetic Susceptibility ° C Degrees Celsius C CDW CI cm -1 Cp Cp* CV δ d.i. DFT DMSO Curie Constant Charge density wave Chemical Ionization Wavenumber Cyclopentadienyl Pentamethylcyclopentadienyl Cyclic Voltametry NMR shift frequency deionized Density functional theory Dimethylsulfoxide xv
Page 1 and 2: 1,2,3-Dithiazolyl and 1,2,35-Dithia
Page 3 and 4: an individual binuclear coordinatio
Page 5 and 6: weren’t sure about something our
Page 7 and 8: 2.1 General........................
Page 9 and 10: 5.3 Reverse oDTANQ.................
Page 11 and 12: LIST OF FIGURES AND SCHEMES Figure
Page 13: Figure 2-12. Magnetic susceptibilit
Page 17 and 18: K k k B LMCT ls LUMO Kelvin Exchang
Page 19 and 20: LIST OF STRUCTURES I-1 I-2 I-3 I-4
Page 21 and 22: I-16a I-16b I-16c I-16d I-16e I-16f
Page 23 and 24: I-22 I-23 I-24 I-25 exo I-26 endo x
Page 25 and 26: I-34 I-35 II-3 II-4 II-1 xxv
Page 27 and 28: III-2 III-1 III-3 III-4 III-5 III-6
Page 29 and 30: V-7 V-8 V-9 V-10 V-11 V-12 V-13 V-1
Page 31 and 32: Chapter 1 - General Introduction 1.
Page 33 and 34: linear relationship shown in Figure
Page 35 and 36: A plot of χT vs. T is an important
Page 37 and 38: examination of phenyl methylene. In
Page 39 and 40: different atomic nuclei. Qualitativ
Page 41 and 42: 3) 14 and a variety of thiazyl base
Page 43 and 44: with one another with an energy bar
Page 45 and 46: magnetic properties and undergoes a
Page 47 and 48: heteroatoms which could facilitate
Page 49 and 50: Figure 1-5. Qualitative molecular o
Page 51 and 52: temperature. 64 This was a very imp
Page 53 and 54: dimerization and therefore a quench
Page 55 and 56: e enough to overcome the energetica
Page 57 and 58: eaches the lower end of the investi
Page 59 and 60: DTDAs has been to exploit the rearr
Page 61 and 62: 1.3.4 1,2,3-Dithiazolyl Radicals (I
Page 63 and 64: aromatic ring not only protects the
Page 65 and 66:
is quite similar to the spin-polari
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compound there are many competing m
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a b c d e Figure 1-16. a) Nonorthog
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would result in non-orthogonal over
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platinum center as well as the phos
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substantial amount of unpaired elec
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I-28 I-29 I-30 The metals manganese
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gave a combination of 2 mononuclear
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changes related to geometric, chemi
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Finally, the last chapter reviews t
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(23) Rajca, A. Chem. Rev. 1994, 94,
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(53) Azuma, N.; Tsutsui, K.; Miura,
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(79) Decken, A.; Cameron, T. S.; Pa
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(102) Herz, R.; Leopold Cassella &
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(128) Aliaga-Alcalde, N., 2003. (12
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Chapter 2 - Structural and Magnetic
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2.2.2 pymDSDA Coordination Complexe
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2.2.3 DTDA Coordination Complexes o
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indicators tend to be very weak str
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In Figure 2-1a, the nickel complex
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2.2.3 Cyclic Voltametry The cyclic
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propensity for intermolecular Se-N
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dimerization motif. One possible ex
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the bridging ligand such that the D
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contacts into four different intera
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e acting as a closed-shell, S = 0,
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2.3.4 [Zn(hfac) 2 ] 2·pymDTDA (II-
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ancillary ligands and the nearly oc
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single molecular unit. Upon closer
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across the entire temperature regim
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2.5 Conclusions and Future Work It
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therefore chain formation. However
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The work presented in this chapter
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736(s), 723(s), 646(s), 632(s), 469
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(0.2023 g, 1.104 mmol) in 30 mL of
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(6) Chattoraj, S. C.; Cupka Jr, A.
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Chapter 3 - 5-oxo-5H-naphtho[1,2-d]
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triethylammonium chloride which was
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3.3.2 Mass Spectrometry A sample of
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3.3.4 X-ray Crystallography Crystal
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a 2-fold screw axis across half of
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number of electrons that this compo
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often generated in situ although wa
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similar to compounds II-1 and II-2,
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3.6 Experimental General All reacti
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Chapter 4 - The Polymorphism of Tri
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4.3 Discussion Prior to the discove
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(derived from angles ranging from 4
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a b c Figure 4-2. Packing diagrams
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polymorphs observed and are therefo
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Chapter 5 5.1 Overview There are se
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success and so a Herz ring closure
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did not immediately precipitate, bu
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Figure 5-2 shows the IR spectra for
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comparison of the infrared data obt
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discussed in section 5.2.2. As the
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ing was formed. One of the nitrogen
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equired to obtain a decent agreemen
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Considerations have been put toward
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chelation pocket is similar to that
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the mixture was filtered to remove
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good spectroscopic handle for this
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spectrum from about 1900 to 400 cm
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doublets of triplets associated wit
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adical, followed by the closed-shel
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completely dry after being under va
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changed substantially after the tra
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The reaction to produce V-15 was qu
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the proton two carbons away next to
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which is parallel to the mean plane
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of the 1,2,3-DTA rings could act as
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mixture was refluxed for 20 h yield
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the heat source was removed and the
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1085(w), 1059(w), 1008(w), 917(w),
Page 213 and 214:
___________________________________
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Crystallography P 2 1 /c a = 9.1678
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Compound Name: 4-(2′-pyrimidyl)-1
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Compound Name: [μ-4-(2′-pyrimidy
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Magnetometry 192
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Crystallography P-1 a = 8.9576, b =
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Compound Name: [μ-4-(2′-pyrimidy
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Magnetometry: 198
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Crystallography: P2 1 /n a = 19.884
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Compound Name: 5-oxo-5H-naphtho[1,2
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204
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206
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MS (EI + ): 208
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Compound Name: 5-chloro-1H-[1,2,5]t
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Compound Name: 3-nitro-1,2-naphthaq
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Compound Name: 3,4-dioxo-3,4-dihydr
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Compound Name: 4,5-dioxo-4,5-dihydr
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Compound Name: 6,6′-dinitro-1,1
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220
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222
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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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