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

More documents

Recommendations

Info

Figure 1-17. a) molecular structure of I-21, b) arrangement of chains of I-21 showing inter-chain contacts...........................................................................................................................................................40 Scheme 2-1. Synthesis of II-4 and II-1 from II-3........................................................................................65 Scheme 2-2. Reaction sheme illustrating coordination of II-1 to give II-5; M = Ni and II-6; M = Mn.......67 Scheme 2-3. Reaction scheme outlining syntheses of the II-7 and II-8 and the different sublimation conditions........................................................................................................................................................68 Figure 2-1. Infrared spectra from 2000 cm -1 to 420 cm -1 of a) II-1, Ni(hfac) 2·2THF and II-5. b) II-1 Mn(hfac) 2·2THF and II-6. c) II-1, Zn(hfac)2·2THF and II-7 d) II-1, Zn(hfac) 2·2THF and II-8............60-71 Figure 2-2. EPR spectra of a) II-1, g = 2.0382, spectral width = 150 G, b) II-7, a N = 4.82, g = 2.038 and c) II-2 a N = 5.12, g = 2.010.................................................................................................................................73 Figure 2-3. Cyclic Voltamagram of II-1 showing individual peak potentials. Oxidative direction to the right, reductive direction to the left................................................................................................................74 Figure 2-4. X-ray crystallographic representation of II-1, showing trans cofacial dimerization.................75 Figure 2-5. ORTEP depictions of the single crystal X-ray structures of a) II-5, b) II-6, c) II-7 and d) II-8 showing 1 molecular unit of each complex demonstrating the local geometry about the metal centers. Thermal ellipsoids at 50%, F and H atoms have been omitted for clarity......................................................76 Figure 2-6. Crystallographic representation of neighboring DSDA nickel complexes II-5 showing close Se...Se contacts. The backbone of the ancillary hfac ligand has been removed for clarity...........................77 Figure 2-7. a) Unit cell of II-6 depicting the ligand disorder and showing the two molecules in the asymmetric unit. b) Linear propagation of Molecule 2 with ligand shown in head-to-tail orientation. c) Linear propagation of Molecule 2 with ligand showing head-to-head and tail-to-tail orientations. The backbone of the ancillary hfac ligands have been removed in all cases for clarity........................................78 Figure 2-8. a) Unit cell of II-7. b) Mononuclear component of II-8 showing intermolecular close S...N contacts...........................................................................................................................................................83 Figure 2-9. DTDA interaction classifications SN-I and SN-IV as well as the new SN-V to describe the interactions in the mononuclear component of II-8 and II-11.......................................................................84 Scheme 2-4. Proposed coupling schemes for a) II-11 and b) II-5.................................................................86 Figure 2-10. Magnetic susceptibility (χT) of II-11 and II-5 as a function of temperature from 300 to 2 K at 1000 Oe...........................................................................................................................................................86 Scheme 2-5. Proposed coupling scheme for II-6 and II-9............................................................................87 Figure 2-11. Magnetic susceptibility (χT) for II-9 and II-6 as a function of temperature from 300 to 2 K at 1000 Oe...........................................................................................................................................................87 xii
Figure 2-12. Magnetic susceptibility (χT) for a) II-7 and b) II-8 as a function of temperature from 300 to 2 K at 1000 Oe...................................................................................................................................................88 Figure 2-13. Intermolecular contacts in II-12 which give rise to sigmoidal χT vs logT data.......................91 Figure 2-14. Pair-wise dimer formation of theoretical manganese complex of II-14..................................98 Figure 2-15. Chain formation of theoretical manganese complex of II-15..................................................99 Scheme 3-1. The synthesis of III-3..............................................................................................................110 Figure 3-1. 1 H NMR spectrum for III-3 in DMSO at 300 MHz. there are some minor impurities..........111 Figure 3-2. IR transmission spectra for III-1 and III-3 with labelled peaks in the carbonyl region..........113 Figure 3-3. ORTEP depiction of III-3. Hydrogens removed for clarity. 50% probability ellipsoids........114 Figure 3-4. Chains of III-3 propgating along the [010] direction by short S-O contacts............................115 Figure 3-5. Unit cell of III-3 viewed down the [100] axis.........................................................................116 Figure 3-6. Cyclic voltammogram of III-3 showing the reversible oxidation with E ½ = 0.95 V, ΔE pp = 120 mV and an irreversible reduction at -0.683 V. CH 3 CN, n Bu 4 PF 6 (0.1 M), 3 mM analyte, 100 mV/s, referenced against SCE with fc/fc + as internal standard set to E ½ = 0.380 V..............................................117 Figure 3-7. Oxidation states of quinone based molecular systems.............................................................118 Figure 4-1. ORTEP depiction of the asymmetric unit of IV-2a showing both crystalographically unique molecules. 50% probability ellipsoids, H atoms omitted for clarity............................................................127 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....................................................132 Scheme 5-1. The reaction used to isolate V-3 from the commercially available starting material V-2......138 Scheme 5-2. The reaction of V-3 with gallium trichloride to give V-4.......................................................139 Scheme 5-3. The reaction of V-3 with NOPF 6 to give V-5.........................................................................140 Figure 5-1. Infrared transmission spectrum of V-2....................................................................................142 Figure 5-2. Infrared transmission spectra of V-3 overlaid with V-2. Peak labels correspond to V-3 only...............................................................................................................................................................143 Figure 5-3. Infrared spectra of a) the gallate salt (V-4) and b) the hexafluorophosphate salt (V-5), both compared to the starting material V-3..........................................................................................................144 Figure 5-4. Infrared spectra of V-1 and overlaid with V-3. Peaks labelled for V-1 only. Note that this does not look simply like a reduction product......................................................................................................145 xiii
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: LIST OF FIGURES AND SCHEMES Figure
Page 15 and 16: GLOSSARY OF ABBREVIATIONS ° Degree
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
Page 67 and 68:
compound there are many competing m
Page 69 and 70:
a b c d e Figure 1-16. a) Nonorthog
Page 71 and 72:
would result in non-orthogonal over
Page 73 and 74:
platinum center as well as the phos
Page 75 and 76:
substantial amount of unpaired elec
Page 77 and 78:
I-28 I-29 I-30 The metals manganese
Page 79 and 80:
gave a combination of 2 mononuclear
Page 81 and 82:
changes related to geometric, chemi
Page 83 and 84:
Finally, the last chapter reviews t
Page 85 and 86:
(23) Rajca, A. Chem. Rev. 1994, 94,
Page 87 and 88:
(53) Azuma, N.; Tsutsui, K.; Miura,
Page 89 and 90:
(79) Decken, A.; Cameron, T. S.; Pa
Page 91 and 92:
(102) Herz, R.; Leopold Cassella &
Page 93 and 94:
(128) Aliaga-Alcalde, N., 2003. (12
Page 95 and 96:
Chapter 2 - Structural and Magnetic
Page 97 and 98:
2.2.2 pymDSDA Coordination Complexe
Page 99 and 100:
2.2.3 DTDA Coordination Complexes o
Page 101 and 102:
indicators tend to be very weak str
Page 103 and 104:
In Figure 2-1a, the nickel complex
Page 105 and 106:
2.2.3 Cyclic Voltametry The cyclic
Page 107 and 108:
propensity for intermolecular Se-N
Page 109 and 110:
dimerization motif. One possible ex
Page 111 and 112:
the bridging ligand such that the D
Page 113 and 114:
contacts into four different intera
Page 115 and 116:
e acting as a closed-shell, S = 0,
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
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 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
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),
Page 213 and 214:
___________________________________
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 =
Page 225 and 226:
Compound Name: [μ-4-(2′-pyrimidy
Page 227 and 228:
Magnetometry: 198
Page 229 and 230:
Crystallography: P2 1 /n a = 19.884
Page 231 and 232:
Compound Name: 5-oxo-5H-naphtho[1,2
Page 233 and 234:
204
Page 235 and 236:
206
Page 237 and 238:
MS (EI + ): 208
Page 239 and 240:
Compound Name: 5-chloro-1H-[1,2,5]t
Page 241 and 242:
Compound Name: 3-nitro-1,2-naphthaq
Page 243 and 244:
Compound Name: 3,4-dioxo-3,4-dihydr
Page 245 and 246:
Compound Name: 4,5-dioxo-4,5-dihydr
Page 247 and 248:
Compound Name: 6,6′-dinitro-1,1
Page 249 and 250:
220
Page 251:
222
show all

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

Create successful ePaper yourself

Delete template?

Save as template?