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

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y flash distillation, and the residue was divided into two portions, each of which was sublimed under a dynamic vacuum at 120 °C (10 −2 Torr), yielding dark-blue needles of II-8 (0.2543 g; 27% yield based on Znhfac 2·2THF) suitable for X-ray crystallography and magnetic measurements. ν max (KBr)/cm −1 : 3138(w), 2961(w), 2914(w), 2851(w), 1647(s), 1586(w), 1560(m), 1532(m), 1487(s), 1463(m), 1389(m), 1348(w), 1319(w), 1259(s), 1208(s), 1150(s), 1137(s), 1097(m), 861(w), 841(w), 813(m), 796(m), 763(w), 743(w), 716(w), 669(m), 647(w), 586(m), 526(w). Anal. Calcd. for C 55 H 17 F 48 Zn 4 N 12 O 16 S 6 : C, 26.76; H, 0.69; N, 6.81%. Found: C, 27.12; H, 0.89; N, 6.75%. X-ray: P 2 1 /n, a = 19.884, b = 8.8599, c = 23.216, β = 100.73, R = 5.09. 2.7 References (1) Preuss, K. E. Dalton Trans. 2007, 2357. (2) Wu, J.; MacDonald, D. J.; Clérac, R.; Jeon Ie, R.; Jennings, M.; Lough, A. J.; Britten, J.; Robertson, C.; Dube, P. A.; Preuss, K. E. Inorg. Chem. 2012, 51, 3827. (3) Jennings, M.; Preuss, K. E.; Wu, J. Chem. Commun. 2006, 341. (4) Cordes, A. W.; Bryan, C. D.; Davis, W. M.; Delaat, R. H.; Glarum, S. H.; Goddard, J. D.; Haddon, R. C.; Hicks, R. G.; Kennepohl, D. K.; Oakley, R. T.; Scott, S. R.; Westwood, N. P. C. J. Am. Chem. Soc. 1993, 115, 7232. (5) Cordes, A. W.; Glarum, S. H.; Haddon, R. C.; Hallford, R.; Hicks, R. G.; Kennepohl, D. K.; Oakley, R. T.; Palstra, T. T. M.; Scott, S. R. Chem. Commun. 1992, 1265. 105
(6) Chattoraj, S. C.; Cupka Jr, A. G.; Sievers, R. E. J. Inorg. Nuc. Chem. 1966, 28, 1937. (7) Preuss, K. E.; Wu, J.; Jennings, M. Acta Cryst. 2005, E61, M430. (8) Del Bel Belluz, P.; Cordes, A. W.; Kristof, E. M.; Kristof, P. V.; Liblong, S. W.; Oakley, R. T. J. Am. Chem. Soc. 1989, 111, 9276. (9) Awere, E.; Passmore, J.; Preston, K. F.; Sutcliffe, L. H. Can. J. Chem. 1988, 66, 1776. (10) Belluz, P. D. B.; Cordes, A. W.; Kristof, E. M.; Kristof, P. V.; Liblong, S. W.; Oakley, R. T. J. Am. Chem. Soc. 1989, 111, 9276. (11) Tsierkezos, N. G. J. Sol. Chem. 2007, 36, 289. (12) Haynes, D. A. Cryst. Eng. Comm. 2011, 13, 4793. (13) Vegas, A.; Pérez-Salazar, A.; Banister, A. J.; Hey, R. G. Dalton Trans. 1980, 1812. (14) Barclay, T. M.; Cordes, A. W.; George, N. A.; Haddon, R. C.; Itkis, M. E.; Oakley, R. T. Chem. Commun. 1999, 2269. (15) Chandrasekhar, V.; Chivers, T.; Fait, J. F.; Kumaravel, S. S. J. Am. Chem. Soc. 1990, 112, 5373. (16) Bond, A. D.; Haynes, D. A.; Pask, C. M.; Rawson, J. M. Dalton Trans. 2002, 2522. 106
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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
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: (0.2023 g, 1.104 mmol) in 30 mL of
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
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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
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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
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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),
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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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222
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1,2,3-Dithiazolyl and 1,2,35-Dithiadiazolyl Radicals as Spin-Bearing ...

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