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

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TABLE OF CONTENTS 1. General Introduction.......................................................................................................1 1.1 Theoretical Consideration for Organic Systems......................................................1 1.1.1 Molecular Magnetism..................................................................................1 1.1.2 Electronic Considerations............................................................................6 1.2 Persistent Organic Radicals...................................................................................10 1.2.1 Triphenyl Methyl Radical..........................................................................11 1.2.2 α-Nitronyl-Nitroxides................................................................................13 1.2.3 Verdazyls...................................................................................................15 1.3 Thiazyl Radicals.....................................................................................................18 1.3.1 Trithiadiazolium Chloride (S 3 N 2·Cl [I-11]) and Related Species..............18 1.3.2 Trithiatrazapentalenyl (TTTA [I-14a])......................................................20 1.3.3 Dithiadiazolyl Radicals and Their Selenium Analogues...........................21 1.3.3.1 1,2,3,5-Dithiadiazolyl Radicals (I-16)...........................................21 1.3.3.2 1,2,3,5-Diselenadiazolyl Radicals (I-18).......................................28 1.3.4 1,2,3-Dithiadiazolyl Radicals (I-17)..........................................................30 1.4 Metal Coordination of Radical Ligands.................................................................33 1.4.1 Magnetic Coupling Between Metal Centers..............................................33 1.4.2 Magnetic Properties of Organic Radical Coorindination Complxes.........37 1.4.3 Coordination Complexes of Thiazyl Radical Ligands...............................39 1.5 Thesis Overview....................................................................................................49 1.6 References..............................................................................................................52 2. Stuctural and Magnetic Properties of Binuclear Coordination Complexes of 4-(2′-pyrimidal)-1,2,3,5-Dithiadiazolyl and 4-(2′-pyrimidal)-1,2,3,5-Diselenadiazolyl Radicals..............................................................................................................................64 vi
2.1 General...................................................................................................................64 2.2 Synthesis................................................................................................................64 2.2.1 pymDSDA Radical....................................................................................64 2.2.2 pymDSDA Coordination Complexes........................................................66 2.2.3 pymDTDA Coordination Complexes of Zinc............................................68 2.3 Characterization.....................................................................................................69 2.3.1 Infrared Spectroscopy................................................................................69 2.3.2 EPR............................................................................................................72 2.3.3 Cyclic Voltametry......................................................................................74 2.3.4 X-ray Crystallography...............................................................................75 2.4 Magnetic Measurements........................................................................................85 2.4.1 pymDSDA (II-1)........................................................................................85 2.4.2 [Ni(hfac) 2 ] 2·pymDSDA (II-5)....................................................................85 2.4.3 [Mn(hfac) 2 ] 2·pymDSDA II-6.....................................................................86 2.4.4 [Zn(hfac) 2 ] 2·pymDTDA (II-7) and [Zn(hfac) 2 ] 2·pymDTDA 2Zn(hfac) 2 ·pymDTDA (II-8).....................................................................................................88 2.5 Discussion..............................................................................................................89 2.6 Conclusions and Future Work...............................................................................96 2.7 Experimental........................................................................................................100 2.8 References............................................................................................................105 3. 5-Oxo-5H-naphtho[1,2-d][1,2,3]dithiazol-4-yl acetate..............................................108 3.1 General.................................................................................................................108 3.2 Synthesis..............................................................................................................109 3.3 Characterization...................................................................................................110 vii
Page 1 and 2: 1,2,3-Dithiazolyl and 1,2,35-Dithia
Page 3 and 4: an individual binuclear coordinatio
Page 5: weren’t sure about something our
Page 9 and 10: 5.3 Reverse oDTANQ.................
Page 11 and 12: LIST OF FIGURES AND SCHEMES Figure
Page 13 and 14: Figure 2-12. Magnetic susceptibilit
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
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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
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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
Page 85 and 86:
(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
Page 105 and 106:
2.2.3 Cyclic Voltametry The cyclic
Page 107 and 108:
propensity for intermolecular Se-N
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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-
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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
Page 177 and 178:
ing was formed. One of the nitrogen
Page 179 and 180:
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
Page 197 and 198:
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
Page 203 and 204:
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
Page 219 and 220:
Compound Name: [μ-4-(2′-pyrimidy
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Magnetometry 192
Page 223 and 224:
Crystallography P-1 a = 8.9576, b =
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Compound Name: [μ-4-(2′-pyrimidy
Page 227 and 228:
Magnetometry: 198
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Crystallography: P2 1 /n a = 19.884
Page 231 and 232:
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
Page 247 and 248:
Compound Name: 6,6′-dinitro-1,1
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220
Page 251:
222
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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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