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

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some effect on several of the bond lengths which would therefore impact frequency of the absorption associated with the stretches of the bonds that are most affected by the presence of the extra electron. The peak associated with the N-S bond within the new 1,2,3-DTA ring was at 721 cm -1 and has shifted substantially to 680 cm -1 . The weak intensity peak at 1261 cm -1 associated with the N-S stretches of the 1,2,5-TDA ring is not shifted substantially, however the medium intensity peaks at 936 and 584 cm -1 in V-3 have shifted to 913 and 575 cm -1 in V-1 respectively, both lower than in the precursor salt. Similarly, the C-N stretches have shifted form 1482 and 1535 cm -1 in V-3 to 1493 and 1544 cm -1 respectively in V-1. The C-Cl stretch has also shifted from an absorption at 861 cm -1 in V-3 to 814 cm -1 in V-1. Figure 5-4. Infrared spectra of V-1 and overlaid with V-3. Peaks labelled for V-1 only. 5.2.4 X-ray Crystallography The only compound for which X-ray crystallography quality crystals were obtained was V-4. They were grown from a combination of acetonitrile and chlorobenzene as 145
discussed in section 5.2.2. As the solvent was removed rather quickly, the crystals that were formed were not very good quality and resulted in a highly disordered structure. The tetrahedral tetrachlorogallate anion was found to have three-fold disorder modeled according to the ORTEP depiction in Figure 5-5 and contains elongated ellipsoids for the chlorine atoms. In addition, the cation was found to be incommensurate. As a consequence, the R value was only able to be minimized to 12.06%. With such a large R value there was some doubt cast on the nature of the compound isolated. It should however be noted that the substituent was confirmed by EI/MS to be a chlorine atom from the chloride salt (V-3) and from the gallate salt (V-4) both giving an m/z of 245.9 and the isotopic distribution anticipated for one chlorine atom. Figure 5-5. Ortep depiction of V-4 showing three-fold disordered tetrachlorogallate anion. Ellipsoids are 50%, H atom assigned isotropically. In addition to the target tetrachlorogallate salt, another compound was identified from the same crystalline sample investigated (V-6). This compound was also a 146
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1,2,3-Dithiazolyl and 1,2,35-Dithia
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an individual binuclear coordinatio
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weren’t sure about something our
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2.1 General........................
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5.3 Reverse oDTANQ.................
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LIST OF FIGURES AND SCHEMES Figure
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Figure 2-12. Magnetic susceptibilit
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GLOSSARY OF ABBREVIATIONS ° Degree
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K k k B LMCT ls LUMO Kelvin Exchang
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LIST OF STRUCTURES I-1 I-2 I-3 I-4
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I-16a I-16b I-16c I-16d I-16e I-16f
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I-22 I-23 I-24 I-25 exo I-26 endo x
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I-34 I-35 II-3 II-4 II-1 xxv
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III-2 III-1 III-3 III-4 III-5 III-6
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V-7 V-8 V-9 V-10 V-11 V-12 V-13 V-1
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Chapter 1 - General Introduction 1.
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linear relationship shown in Figure
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A plot of χT vs. T is an important
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examination of phenyl methylene. In
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different atomic nuclei. Qualitativ
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3) 14 and a variety of thiazyl base
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with one another with an energy bar
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magnetic properties and undergoes a
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heteroatoms which could facilitate
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Figure 1-5. Qualitative molecular o
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temperature. 64 This was a very imp
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dimerization and therefore a quench
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e enough to overcome the energetica
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eaches the lower end of the investi
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DTDAs has been to exploit the rearr
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1.3.4 1,2,3-Dithiazolyl Radicals (I
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aromatic ring not only protects the
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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
Page 123 and 124: across the entire temperature regim
Page 125 and 126: 2.5 Conclusions and Future Work It
Page 127 and 128: therefore chain formation. However
Page 129 and 130: The work presented in this chapter
Page 131 and 132: 736(s), 723(s), 646(s), 632(s), 469
Page 133 and 134: (0.2023 g, 1.104 mmol) in 30 mL of
Page 135 and 136: (6) Chattoraj, S. C.; Cupka Jr, A.
Page 137 and 138: Chapter 3 - 5-oxo-5H-naphtho[1,2-d]
Page 139 and 140: triethylammonium chloride which was
Page 141 and 142: 3.3.2 Mass Spectrometry A sample of
Page 143 and 144: 3.3.4 X-ray Crystallography Crystal
Page 145 and 146: a 2-fold screw axis across half of
Page 147 and 148: number of electrons that this compo
Page 149 and 150: often generated in situ although wa
Page 151 and 152: similar to compounds II-1 and II-2,
Page 153 and 154: 3.6 Experimental General All reacti
Page 155 and 156: Chapter 4 - The Polymorphism of Tri
Page 157 and 158: 4.3 Discussion Prior to the discove
Page 159 and 160: (derived from angles ranging from 4
Page 161 and 162: a b c Figure 4-2. Packing diagrams
Page 163 and 164: polymorphs observed and are therefo
Page 165 and 166: Chapter 5 5.1 Overview There are se
Page 167 and 168: success and so a Herz ring closure
Page 169 and 170: did not immediately precipitate, bu
Page 171 and 172: Figure 5-2 shows the IR spectra for
Page 173: comparison of the infrared data obt
Page 177 and 178: ing was formed. One of the nitrogen
Page 179 and 180: equired to obtain a decent agreemen
Page 181 and 182: Considerations have been put toward
Page 183 and 184: chelation pocket is similar to that
Page 185 and 186: the mixture was filtered to remove
Page 187 and 188: good spectroscopic handle for this
Page 189 and 190: spectrum from about 1900 to 400 cm
Page 191 and 192: doublets of triplets associated wit
Page 193 and 194: adical, followed by the closed-shel
Page 195 and 196: completely dry after being under va
Page 197 and 198: changed substantially after the tra
Page 199 and 200: The reaction to produce V-15 was qu
Page 201 and 202: the proton two carbons away next to
Page 203 and 204: which is parallel to the mean plane
Page 205 and 206: of the 1,2,3-DTA rings could act as
Page 207 and 208: mixture was refluxed for 20 h yield
Page 209 and 210: the heat source was removed and the
Page 211 and 212: 1085(w), 1059(w), 1008(w), 917(w),
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Page 215 and 216: Crystallography P 2 1 /c a = 9.1678
Page 217 and 218: Compound Name: 4-(2′-pyrimidyl)-1
Page 219 and 220: Compound Name: [μ-4-(2′-pyrimidy
Page 221 and 222: Magnetometry 192
Page 223 and 224: 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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