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

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molecule, resulting in only one enantiomer in the crystal. Polymorph IV-2c has two molecules in the asymmetric unit and while one of them possesses the same propellertype arrangement of the phenyl substituents, one phenyl ring of the other molecule is nearly perpendicular to the trigonal plane of the molecule. Polymorph IV-2d contains four crystalographically unique molecules in the asymmetric unit and is therefore quite a bit more complex than the others. None of the molecules correspond to the simple propeller-type arrangement exhibited in IV-2b. The two molecules containing the Sb1 and Sb4 respectively have one phenyl ring each which is nearly parallel to the molecular plane of the molecule. Also, the only molecule which has all of the phenyl rings tilted in the same direction is that which contains Sb4. The new polymorph IV-2a contains 2 molecules in the asymmetric unit and neither one has a simple propeller-type arrangement. A phenyl ring of one of the molecules is nearly coincident with the mean plane of the molecule and the rings that are twisted out of the plane are not twisted in the same direction. The packing for polymorphs IV-2a, IV-2b and IV-2d is shown in Figure 4-2. IV-2c has not been included due to the fact that the lattice was complicated due to Cl/F disorder and therefore is not considered to be a pure sample of the IV-2. The new polymorph IV-2a shows columnar packing along the [010] direction with each column being composed of crystalographically identical molecules. The spacing between the molecules within the column is one unit cell length 10.0348(3) Å. The compound IV-2b, which was the first reported, shows similar columnar packing, this time along the [100] direction. 131
a b c Figure 4-2. Packing diagrams for a) IV-2a viewed down the b axis showing the Sb1 containing molecule and Sb2 containing molecule packed in columns. b) IV-2b viewed down the a axis c) IV-2d viewed down the c axis, showing the two different ways that the molecular pairs pack. The spacing between the molecules in the columns is once again equal to one unit cell length (10.882(4) Å) such that there are no close contacts between neighbouring molecules. With four molecules in the asymmetric unit and the largest unit cell of any of the observed polymorphs, IV-2d is much more complicated than any of its higher symmetry counterparts. While this lattice is still composed of columnar arrays as those seen in IV-2a and IV-2b, the columns here are made up of alternating Sb1 containing molecules and Sb4 containing molecules propagating along the [001] direction spaced by 132
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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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Page 117 and 118: 2.3.4 [Zn(hfac) 2 ] 2·pymDTDA (II-
Page 119 and 120: ancillary ligands and the nearly oc
Page 121 and 122: 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
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Page 135 and 136: (6) Chattoraj, S. C.; Cupka Jr, A.
Page 137 and 138: Chapter 3 - 5-oxo-5H-naphtho[1,2-d]
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Page 141 and 142: 3.3.2 Mass Spectrometry A sample of
Page 143 and 144: 3.3.4 X-ray Crystallography Crystal
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Page 147 and 148: number of electrons that this compo
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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: (derived from angles ranging from 4
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 and 174: comparison of the infrared data obt
Page 175 and 176: discussed in section 5.2.2. As the
Page 177 and 178: ing was formed. One of the nitrogen
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Page 189 and 190: spectrum from about 1900 to 400 cm
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1085(w), 1059(w), 1008(w), 917(w),
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___________________________________
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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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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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