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

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1384(s), 1373(m), 1353(w), 1313(s), 1254(w), 1206(m), 1182(s), 1153(w), 1096(w), 1040(m), 1018(m), 964(w), 860(w), 815(s), 770(s), 727(w), 689(m), 672(m), 637(m), 618(w), 600(m), 584(m), 543(m), 486(w), 473(m), 419(w). 1 HNMR (300 MHz, DMSOd 6 ): δ 8.44 (d, J = 9.0 Hz, 1H), δ 8.16 (d, J = 9.3 Hz, 1H), δ 7.87 (m, 2H), δ 2.37 (s, 3H). MS (EI + ): m/z = 277.02 (parent ion) 235.00 (-C 2 H 2 O), 207.00, 177.99, 130.05, 103.06, 76.01. X-ray: P2 1 /n, a: 4.7207(5), b: 13.3232(13), c: 18.4301(18), β: 92.977(2). CV: (3 mM analyte; 0.1 M [ n Bu 4 N][PF 6 ] electrolyte; the fc/fc + couple at E 1/2 = 0.40 V vs SCE as the internal standard) A reversible oxidative process E 1/2 = 0.95 V vs SCE (ΔE pp = 120 mV) and an irreversible reductive process E red = −0.68 V vs SCE were revealed. 3.7 References (1) Smithson, C., M.Sc. Thesis, University of Guelph, 2011. (2) Cheung, H.; Tanke, R. S.; Torrence, G. P. In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000. (3) Uchimiya, M.; Stone, A. T. Chemosphere 2009, 77, 451. (4) Evangelio, E.; Ruiz-Molina, D. C. R. Chim. 2008, 11, 1137. (5) Sato, O. J. Photochem. Photobiol., C 2004, 5, 203. (6) Guetlich, P.; Hauser, A.; Spiering, H. Angew. Chem. Int. Ed. Engl. 1994, 106, 2109. (7) Sato, O.; Tao, J.; Zhang, Y.-Z. Angew. Chem., Int. Ed. Eng. 2007, 46, 2152. 125
Chapter 4 - The Polymorphism of Triphenylantimony Dichloride 4.1 General Triphenylantimony (IV-1) is a very useful reducing agent for DTDAs and DSDAs. 1 There has also been some success using it as a reducing agent for DTA-containing chloride salts as precursors for their respective neutral radicals. 2 As a preliminary investigation of 5-chloro-1H-[1,2,5]thiadiazolo[3,4-e][1,2,3]benzodithiazolium chloride a reduction was attempted with triphenylantimony. The filtrate was concentrated down in an attempt to obtain crystals of the desired radical product 5-chloro-1H- [1,2,5]thiadiazolo[3,4-e][1,2,3]benzodithiazolyl. Small crystals, covered in amorphous dark powder were obtained and analyzed by X-ray crystallography and were determined to be not the target species, but the byproduct of this reaction, triphenylantimony dichloride (IV-2). The amorphous powder covering the crystals made it difficult to see that they were of the clear and colourless nature anticipated for this byproduct. The X- ray analysis showed that the plate crystal habit of the compound was one that had hitherto not been reported, although several other polymorphs were known. While only a side product of the reactions of primary interest in this thesis, IV-1 is commercially available and it can be used as a starting material for organostibene chemistry 3 as well as for multinuclear antimony complexes. 4 It has also been used to generate carboxylate containing antimony complexes 5,6 which are of particular interest as they have been shown to exhibit anti-tumor activity. 5 Compound IV-2 has also been shown to form condensation polymers with Lewis bases which can act as strong antibacterial agents 7 and it has also been suggested that these compounds could be used as anti-cancer drugs. 8 This chapter will review data associated with the new polymorph as 126
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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
Page 103 and 104: In Figure 2-1a, the nickel complex
Page 105 and 106: 2.2.3 Cyclic Voltametry The cyclic
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Page 113 and 114: contacts into four different intera
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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 153: 3.6 Experimental General All reacti
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
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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 185 and 186: the mixture was filtered to remove
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Page 189 and 190: spectrum from about 1900 to 400 cm
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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),
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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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