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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 王 瑜 | |
dc.contributor.author | Ching-Yi Wei | en |
dc.contributor.author | 魏景怡 | zh_TW |
dc.date.accessioned | 2021-06-13T15:21:19Z | - |
dc.date.available | 2013-07-30 | |
dc.date.copyright | 2008-07-30 | |
dc.date.issued | 2008 | |
dc.date.submitted | 2008-07-21 | |
dc.identifier.citation | (a) Pauling, L. J. Am. Chem. Soc. 1932, 54, 988-1003. (b) Pauling, L. The nature of the chemical bond, 2nd edn.; Oxford University Press, London, 1940.
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Trans. Faraday Soc. 1961, 57, 198-203. (b) Figgis, B. N. Trans. Faraday Soc. 1961, 57, 204-209. Marchivie, M.; Guionneau, P.; Howard, J. A. K.; Goeta, A. E.; Chastanet, G.; Létard, J. F.; Chasseau, D. J. Am. Chem. Soc. 2002, 124, 194-195. Hayami, S.; Gu, Z. Z.; Yoshiki, H.; Fujishima, A.; Sato, O. J. Am. Chem. Soc. 2001, 123, 11644-11650. Takahashi, K.; Cui, H. B.; Okano, Y.; Kobayashi, H.; Einaga, Y.; Sato, O.; Inorg. Chem. 2006, 45, 5739-5741. Timken, M. D.; Strouse, C. E.; Soltis, M. S.; Daverio, S. A.; Hendrickson, D. N.; Abdel-Mawgoud, A. M.; Wilson, S. R. J. Am. Chem. Soc. 1986, 108, 395-402. Conti, A. J.; Chadha, R. K.; Sena, K. M.; Rheingold, A. L.; Hendrickson, D. N. Inorg. Chem. 1993, 32, 2670-2680. Sim, P. G.; Sinn, E.; Petty, R. H.; Merrill, C. L.; Wilson, L. J. Inorg. Chem. 1981, 20, 1213-1222. Timken, M. D.; Hendrickson, D. N.; Sinn, E. Inorg. Chem. 1985, 24, 3947-3955. Costes, J. P.; Dahan, F.; Laurent, J. P. Inorg. Chem. 1990, 29, 2448-2452. 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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/37204 | - |
dc.description.abstract | 本研究為鐵三價自旋交叉 (spin crossover) 錯合物{[Fe(3-OMe-salMen)2]2 [Ni(mnt)2] • xCH3CN}(x=0, 2)合成、結構鑑定與磁性研究之相關探討。{[Fe(3-OMe-salMen)2]2 [Ni(mnt)2] • xCH3CN}有三種不同型態 (polymorph):A含兩個結晶溶劑分子 (x = 2),而B和C不含任何結晶溶劑 (x = 0)。其中A的空間群屬於triclinic Pī,晶格參數為a = 9.402(2), b = 10.476(2), c = 16.636(3) Å,α = 87.17(3),β = 77.38(3),γ = 75.21(3) º;B的空間群屬於triclinic Pī, 晶格參數為a = 10.519(2),b = 10.797(2),c = 13.698(3) Å,α = 100.16(3),β = 100.48(3),γ = 99.80(3) º;C的空間群屬於monoclinic P21/n,晶格參數為a = 9.5747(19),b = 24.916(5),c = 12.404(3) Å,α = 90,β = 102.52(3),γ = 90 º。正一價錯合陽離子{[Fe(3-OMe-salMen)2]+}是由兩個三牙基 (3-OMe-salMen) 的兩個氮原子和一個氧原子與中心三價鐵離子以八面體 (N4O2) 形式配位成;而負二價錯合陰離子 {[Ni(mnt)2]2-} 是兩個雙牙基 (mnt;C2N2S2) 的兩個硫原子與中心鎳離子以平面四方配位而成。
A在溫度5至350 K範圍為低自旋狀態 (low spin, S = 1/2),而B與C呈現緩漸 (gradual) 的自旋轉換現象,自旋轉換溫度 (T1/2) 分別為290 K與120 K。依據熱重分析、磁性測量的結果發現,在溫度超過360 K時,A中結晶溶劑 (CH3CN) 可被移除,轉變為B為高自旋狀態 (high spin, S = 5/2),且A、B間的結晶溶劑吸脫附特性與磁性性質轉變為可逆反應,並且可進一步從X光粉末繞射結果證明。此外,當A在移除結晶溶劑時施以外加壓力,A會轉變為C,且其間的轉變過程不具可逆性。 A、B與C晶體結構的陽離子層與陰離子層交錯排列情形非常相似。A與B的相鄰陽離子間藉由配位基的苯環間π-π作用力形成二聚物 (dimer),而C的陽離子則因相鄰配位基間的近作用力 (short contact) 而形成一維鏈狀結構。由A與B的晶體堆疊相似性可以進一步確認兩者間的可逆反應是容易進行的,而C的晶體堆疊與A的差異性大,推測其間轉變的不可逆特性亦與此有關,且不同的晶體排列亦伴隨著不同之磁性性質。 | zh_TW |
dc.description.abstract | A cationic Fe(III) complex, [Fe(3-OMe-salMen)2]+, forms crystals with Ni(II) complex anion [Ni(mnt)2]2- in three forms in formula of [Fe(3-OMe-salMen)2]2 [Ni(mnt)2] • xCH3CN, (3-OMe-salMen = 2-({[2-(methyl-amino)ethyl]imino} methyl)-3-methoxyphenol; mnt = maleonitriledithiolate) where x =2 is designated as form A; x = 0 for other two forms (B and C). All three crystal structures are characterized by single crystal diffraction method. A belongs to triclinic space group, Pī, with cell parameters a = 9.402(2), b = 10.476(2), c = 16.636(3) Å, α = 87.17(3), β = 77.38(3) and γ = 75.21(3) º; B also belongs to triclinic space group, Pī, with cell parameters a = 10.519(2), b = 10.797(2), c = 13.698(3) Å, α = 100.16(3), β = 100.48(3) and γ = 99.80(3) º; C belongs to monoclinic space group, P21/n, with cell parameters a = 9.5747(19), b = 24.916(5), c = 12.404(3) Å, α = 90, β = 102.52(3) and γ = 90 º. The cation is an octahedrally coordinated (N4O2) iron(III) complex; the anion is a square planar nickel(II) complex. Iron(III) is coordinated by two tridentate ligands, 3-OMe-salMen. According to magnetic measurement, the iron(III) (d5) in A is at the low spin state (LS, S = 1/2) in the temperature range of 5~350 K, while B and C display a gradual spin transition between high spin (HS, S = 5/2) (6A1g) and low spin state (LS, 2T2g) with T1/2 ~ 290 K and 120 K, respectively. Based on the TGA, SQUID and in-situ powder XRD results, the solvent molecule CH3CN in A can be removed by heating at temperature higher than 360 K; meanwhile the spin state of iron(III) changes from LS to HS. B can be obtained from A by removing all the solvent molecules, CH3CN, from the lattice; however the process is completely reversible and accompanied with the structure change as evidenced by the in-situ X-ray powder diffraction. Furthermore, C can be obtained from A during the solvate extraction process with an external pressure. In contrary to the reversible transformation between A and B, the transformation from A to C is irreversible, and the phase transition from B to C is not found. The crystal packing of complex A, B and C are analogously arranged by alternate layers of complex cations and anions. The cations in complex A and B form dimer like pairs via π-π interaction of the phenyl rings of the ligands. As for C, such dimer like pairs no longer exist, the packing is quite different from those of A and B. It is plausible that the different molecular packing may cause the significant shift in magnetic transition temperature. | en |
dc.description.provenance | Made available in DSpace on 2021-06-13T15:21:19Z (GMT). No. of bitstreams: 1 ntu-97-R95223086-1.pdf: 3201180 bytes, checksum: ef28df472fa9988bbb68f3de39e61da3 (MD5) Previous issue date: 2008 | en |
dc.description.tableofcontents | 謝誌 I
中文摘要 II ABSTRACT IV LIST OF FIGURES VIII LIST OF TABLES XII CHAPTER 1 INTRODUCTION 1 1.1 Introduction of Spin Crossover 1 1.1.1 A Brief History 1 1.1.2 Crystal Field Theory 3 1.1.3 Spin Crossover Phenomenon 4 1.2 Iron (III) Spin Crossover Compounds 7 1.2.1 Tris(N,N-Disubstituted-Dithiocarbamato) Iron(III) Compounds 7 1.2.2 Iron(III) Spin Crossover Systems of Tridentate N2O Donating Schiff Base Ligands. 8 1.3 Research Motivation 13 CHAPTER 2 EXPERIMENTAL 17 2.1 Chemicals 17 2.2 Synthesis 18 2.2.1 Synthesis of (Bu4N)2 Ni(mnt)2 18 2.2.2 Synthesis of [Fe(3-OMe-salMen)2]Cl 18 2.2.3 Synthesis of [Fe(3-OMe-salMen)2]2[Ni(mnt)2]•2CH3CN (A) 19 2.2.4 Synthesis of [Fe(3-OMe-salMen)2]2[Ni(mnt)2] (B) 19 2.2.5 Synthesis of [Fe(3-OMe-salMen)2]2[Ni(mnt)2] (C) 20 2.3 Physical Measurements 21 2.3.1 Magnetic property measurement 21 2.3.2 Thermogravimetric analysis 22 2.3.3 X-ray absorption spectrum 22 2.3.4 Powder X-ray diffraction 24 2.3.5 X-ray Single Crystal Crystallography 25 CHAPTER 3 RESULTS AND DISCUSSION 27 3.1 Magnetic Properties 27 3.1.1 The reversibility between polymorph A and B 27 3.1.2 The unexpected two-step magnetic behavior 32 3.1.3 The magnetic properties and powder patterns of polymorph A, B and C 36 3.1.4 Pressure Effect 39 3.2 Electronic Configuration of Fe(III) 43 3.2.1 Fe K-edge absorption spectra 43 3.2.2 Fe LII III-edge absorption spectra 44 3.3 Molecular and Crystal Structures 49 3.3.1 The structure of [Fe (3-OMe-salMen)2]2[Ni(mnt)2]•2CH3CN (A) 49 3.3.2 The structure of [Fe (3-OMe-salMen)2]2[Ni(mnt)2] (B) 54 3.3.3 The structure of [Fe(3-OMe-salMen)2]2[Ni(mnt)2] (C) 59 3.3.4 Comprehensive Comparison 62 CHAPTER 4 CONCLUSIONS 70 APPENDIX 73 REFERENCE 89 | |
dc.language.iso | en | |
dc.title | [Fe(3-OMe-salMen)2]2[Ni(mnt)2]•x CH3CN鐵三價 自旋交叉錯合物之合成、結構鑑定與磁性研究 | zh_TW |
dc.title | Structure and magnetic properties of an iron (III) spin crossover compound: [Fe(3-OMe-salMen)2]2[Ni(mnt)2]•x CH3CN | en |
dc.type | Thesis | |
dc.date.schoolyear | 96-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 魏和祥,許火順,王志傑 | |
dc.subject.keyword | 鐵三價,自旋交叉,磁性, | zh_TW |
dc.subject.keyword | Iron (III),spin crossover,magnetic property, | en |
dc.relation.page | 92 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2008-07-23 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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