在本篇論文中，我們發表了合成雙鉻多重鍵錯合物的新方法。我們還原Cr2(u-Cl)2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2(THF)2 (1)進而得到了Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 (2)和 Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 (3)。我們進一步以KC8來還原3，得到了[K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} (4) (鉻-鉻鍵長， 1.7397(9) Å)。錯合物2、3、4均以核磁共振光譜學、元素分析儀以及X光單晶繞射進行鑑定。錯合物2和4為逆磁性的錯合物並具有鉻-鉻五重鍵的性質。另一方面，我們也合成出一系列雙鉻五重鍵錯合物Cr2[ArNCRNAr]2 (Ar = 2,4,6-Me3C6H2, R = H 8; Ar = 2,6-Et2C6H3, R = H 10; Ar = 2,6-i-Pr2C6H3, R = H 12; Ar = 2,6-i-Pr2C6H3, R = CH3 14)，鉻-鉻鍵長為1.7395(7)-1.812(2) Å。錯合物8，10，12，14均以核磁共振光譜學、元素分析儀以及X光單晶繞射進行鑑定。簡而言之，我們成功地合成出對稱性為D3h和D2h的雙鉻五重鍵錯合物。另一方面，我們合成出了非平行平面雙鉻四重鍵錯合物Cr2{u-[(2-ClC6H4)NCH(tBu)N(2-ClC6H4)]Li}2{u-[(2-ClC6H4)NCH(tBu)N(2-ClC6H4)]} 16。
In this thesis, we report the syntheses and characterizations of multiply bonded dichromium complexes. Upon reduction of Cr2(□-Cl)2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2(THF)2 (1) with KC8, two quintuply-bonded dinuclear chromium complexes Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 (2) and Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 (3) were isolated. Subsequent reduction of 3 with KC8 in the presence of cryptand-[2.2.2] led to the formation of a quintuply-bonded Cr(I)2 compound [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} (4) (Cr-Cr, 1.7397(9) Å) . Complexes 2, 3, 4 have been characterized by NMR, elemental analysis and X-ray diffraction. Complexes 2 and 4 are diamagnetic and they both feature a Cr-Cr quintuple bond. Furthermore, we also synthesized a family of Cr2[ArNCRNAr]2 (Ar = 2,4,6-Me3C6H2, R = H 8; Ar = 2,6-Et2C6H3, R = H 10; Ar = 2,6-i-Pr2C6H3, R = H 12; Ar = 2,6-i-Pr2C6H3, R = CH3 14), which all display a Cr-Cr quintuple bond with Cr-Cr bond lengths in the range of 1.7395(7)-1.812(2) Å. Complexes 8, 10, 12, 14 have been characterized by NMR, elemental analysis and X-ray diffraction. In conclusion, we successfully synthesized two types of quintuply-bonded Cr-Cr complexes, the D3h symmetry complex (4) and D2h symmetry complexes (2, 8, 10, 12, 14). In addition, we isolated an unusual quadruply-bonded Cr(II)2 complex , Cr2{u-[(2-ClC6H4)NCH(tBu)N(2-ClC6H4)]Li}2{u-[(2-ClC6H4)NCH(tBu)N(2-ClC6H4)]} (16) with a nonparallel square planes of each Cr.
英文摘要------------------------------------------------------------------------------------------I
中文摘要----------------------------------------------------------------------------------------III
謝誌----------------------------------------------------------------------------------------------IV
章節目錄
第一章 前言----------------------------------------------------------------------------------p. 1
1-1. 從配位化學到金屬-金屬多重鍵----------------------------------------------------p. 1
1-2. 配基的選擇-----------------------------------------------------------------------------p. 3
1-3. 雙鉻金屬錯合物-----------------------------------------------------------------------p. 4
1-4. 非平行平面雙鉻四重鍵錯合物----------------------------------------------------p. 11
1.5 金屬-金屬四重鍵到金屬-金屬五重鍵---------------------------------------------p. 13
1-6. 蝕相M2L6錯合物(燈籠型錯合物)-------------------------------------------------p. 19
1-7. 研究方向-------------------------------------------------------------------------------p. 20
第二章 實驗結果與討論------------------------------------------------------------------p. 21
2-1. 合成方法(學)的確立-----------------------------------------------------------------p. 21
2-1-1. M2L6燈籠型雙鉻錯合物-----------------------------------------------------------p. 21
2-1-2. M2L4雙鉻錯合物--------------------------------------------------------------------p. 23
2-1-2-1. 從鉻(II)到鉻(I)-------------------------------------------------------------------p. 23
2-1-2-2. 從鉻(III)到鉻(I)------------------------------------------------------------------p. 23
2-1-3. 非平行平面雙鉻四重鍵錯合物--------------------------------------------------p. 25
2-2. 結構解析-------------------------------------------------------------------------------p. 26
2-2-1. M2L6燈籠型雙鉻錯合物-----------------------------------------------------------p. 26
2-2-1-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3---------------------------------p. 26
2-2-1-2. [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4-----p. 28
2-2-2. 雙鉻(II)金屬錯合物----------------------------------------------------------------p. 30
2-2-2-1. Cr2(□-Cl)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2(THF)2 6------------p. 30
2-2-3. 鉻(III)金屬錯合物------------------------------------------------------------------p. 32
2-2-3-1. CrCl2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)](THF)2 11--------------------p. 32
2-2-4. M2L4雙鉻(I)錯合物-----------------------------------------------------------------p. 33
2-2-4-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2THF 2a----------------------p. 33
2-2-4-2.Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2-methylTHF 2b--------------p. 34
2-2-4-3.Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ □-□4-C7H8 2c -----------------p. 36
2-2-4-4.Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 8------------------------------p. 38
2-2-4-5.Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 ∙ 2THF 10a------------------------p. 39
2-2-4-6.Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 10b----------------------------------p. 41
2-2-4-7.Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12--------------------------------p. 42
2-2-4-8. Cr2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)]2 14--------------------------p. 43
2-2-5. 非平行平面雙鉻四重鍵錯合物--------------------------------------------------p. 46
2-2-5-1. Cr2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]Li}2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]} 16-------------------------------------------------------------------------------------------p. 46
2-2-6. UV-vis 光譜-------------------------------------------------------------------------p. 48
2-2-6-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3 (以四氫呋喃當溶劑)-------p. 48
2-2-6-2. [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4 (以四氫呋喃當溶劑)---------------------------------------------------------------------------------p. 48
2-2-6-3. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 2 (以四氫呋喃當溶劑)-------p. 50
2-2-6-4. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 8 (以正己烷當溶劑)-----p. 50
2-2-6-5. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 10 (以正己烷當溶劑)-----------p. 51
2-2-6-6. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12 (以四氫呋喃當溶劑)----p. 51
2-2-6-7. Cr2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)]2 14 (以四氫呋喃當溶劑)---------------------------------------------------------------------------------------------p. 52
2-3. DFT 理論計算-------------------------------------------------------------------------p. 53
2-3-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3------------------------------------p. 53
2-3-2. [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4
-------------------------------------------------------------------------------------------------p. 54
2-3-3. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12---------------------------------p. 55
2-4. 其他嘗試-------------------------------------------------------------------------------p. 56
2-4-1. 還原VCl2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)](THF)2--------------------p. 56
2-4-2. 將配基換成[ArNNNAr]-----------------------------------------------------------p. 57
2-4-3. 還原Cr¬2(□-Cl)[(o-ClC6H4)NCHN(o-ClC6H4)]3 15----------------------------p. 57
第三章 實驗部份---------------------------------------------------------------------------p. 59
3-1. 一般實驗部份-------------------------------------------------------------------------p. 59
3-2. 配基的合成----------------------------------------------------------------------------p. 61
3-3. 去質子化配基的合成----------------------------------------------------------------p. 62
3-3-1. Li(THF)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)] (L2)---------------------p. 62
3-3-2. Li[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)] (L5)-----------------------------p. 63
3-4. 錯合物的合成-------------------------------------------------------------------------p. 64
3-4-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 (2) 以1為起始物---------------p. 64
3-4-2. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 (2) 以5為起始物---------------p. 65
3-4-3. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 (3)----------------------------------p. 65
3-4-4. [K(cryptand[2.2.2])]Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 (4)----------p.66
3-4-5. CrCl2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)](THF)2 (5)-----------------------p. 67
3-4-6. Cr2(□-Cl)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2(THF)2 (6)------------p. 67
3-4-7. CrCl2[(2,4,6-Me3C6H3)NCHN(2,4,6-Me2C6H3)](THF)2 (7)-------------------p. 68
3-4-8. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 (8) 以7為起始物-----------p. 69
3-4-9. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 (8) 以6為起始物-----------p. 69
3-4-10. CrCl2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)](THF)2 (9)------------------------p. 70
3-4-11. Cr2[(2,6-Et2C¬6H3)NCHN(2,6-Et2C6H3)]2 (10)----------------------------------p. 71
3-4-12. CrCl2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)](THF)2 (11)-------------------p. 71
3-4-13. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 (12)------------------------------p. 72
3-4-14. CrCl2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)](THF)2 (13)--------------p. 73
3-4-15. Cr2[(2,6-i-Pr2C6H3)NC(CH3)(2,6-i-Pr2C6H3)]2 (14)---------------------------p. 74
3-4-16. Cr2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]Li}2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]} (16)-----------------------------------------------------------------------------------------p. 75
第四章 結論---------------------------------------------------------------------------------p. 76
第五章 參考文獻---------------------------------------------------------------------------p. 78
第六章 附錄---------------------------------------------------------------------------------p. 80
6-1. 磁性資料-------------------------------------------------------------------------------p. 80
6-1-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3的固態磁性資料 (2-300 K, 5000 Gauss)-----------------------------------------------------------------------------------------p. 80
6-1-2. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 2的固態磁性資料 (2-300 K, 5000 Gauss)-----------------------------------------------------------------------------------------p. 80
6-1-3. Cr2(□-Cl)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2(THF)2 6的固態磁性資料(2-300 K, 5000 Gauss)-------------------------------------------------------------------p. 81
6-2單晶結構資料---------------------------------------------------------------------------p. 82
6-2-1. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2THF 2a ------------------------p. 82
6-2-2. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2-methylTHF 2b ---------------p. 83
6-2-3. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ □-□4-C7H8 2c -------------------p. 84
6-2-4. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3------------------------------------p. 85
6-2-5. [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4-------p. 86
6-2-6. Cr2(□-Cl)2[2,4,6-Me3C6H2NC(H)N(2,4,6-Me3C6H2)]¬2(THF)2 6--------------p. 87
6-2-7. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]¬2 8-------------------------------p. 88
6-2-8. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 ∙ 2THF 10a--------------------------p. 89
6-2-9. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 10b-----------------------------------p. 90
6-2-10. CrCl2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)](THF)2 11---------------------p. 91
6-2-11. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12--------------------------------p. 92
6-2-12. Cr2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)]2 14---------------------------p. 93
6-2-13. Cr2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]Li}2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]} 16-------------------------------------------------------------------------------------------p. 94
圖表目錄
圖1-1. [Re2Cl8]-與Mo2[(O2CCH3)4]2-結構圖---------------------------------------------p. 1
圖1-2. 金屬-金屬四重鍵的d軌域交互作用示意圖-----------------------------------p. 2
圖1-3. 常見的配基--------------------------------------------------------------------------p. 3
方程式1-1. Cr2(O2CCH3)4的合成---------------------------------------------------------p. 4
方程式1-2. 風車型雙鉻金屬錯合物的合成--------------------------------------------p. 5
方程式1-3. Cr2[2,6-(MeO)2C6H3]4的合成------------------------------------------------p. 5
方程式1-4. Cr2[2,6-(MeO)2C6H3]4的合成-----------------------------------------------p. 6
圖1-4. Cr2[MeNC(Ph)NMe]4的分子結構圖---------------------------------------------p. 7
圖1-5. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2(O2CCH3)2(THF)2的分子結構圖---------------------------------------------------------------------------------------------------p. 8
圖1-6. Cr2(□-Cl)2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2(THF)2的分子結構圖---p. 8
圖1-7. Cr[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2的分子結構圖---------------------p. 9
圖1-8. Cr[(2,6-i-Pr2C6H3)NC(Ph)N(2,6-i-Pr2C6H3)]2的分子結構圖-----------------p. 9
圖1-9. Cr2[[(o-ClC6H4)NCHN(o-ClC6H4)]4的分子結構圖---------------------------p. 10
圖1-10. Cr2(□-Cl)[ (o-BrC6H4)NCHN(o-BrC6H4)]3的分子結構圖------------------p. 10
圖1-11. amidinate的結構圖---------------------------------------------------------------p. 11
圖1-12. LCr2Me2(□-Me) (L = 1,1’-methylene-3,3’-di-2,6-diisopropylphenylimidazole-2,2’-diylidene)的分子結構圖-------------------------------------------------------------------------------------------------p. 12
圖1-13. 非平行平面金屬-金屬四重鍵的d軌域交互作用示意圖-----------------p. 12
圖1-14. Hoffmann所提出的金屬-金屬五重鍵d軌域交互作用示意圖-----------p. 13
圖1-15. 金屬-金屬五重鍵鍵結模式圖-------------------------------------------------p. 14
圖1-16. 金屬-金屬四重鍵鍵結模式圖-------------------------------------------------p. 15
方程式1-5. Mo2[2,6-i-Pr2C6H3NSiMe2] [□-□□-2-Me2Si(NDipp)2]2的合成---------p. 16
圖1-17. Mo2[2,6-i-Pr2C6H3NSiMe2] [□-□□-2-Me2Si(NDipp)2]2的HOMO與HOMO-11之結構圖------------------------------------------------------------------------p. 16
圖1-18. Cr2[2,6-(2,6-i-Pr2C6H3)2C6H3]2的結構圖-------------------------------------p. 17
圖1-19. Cr2[(2,6-i-Pr2C6H3)NCHCHN(2,6-i-Pr2C6H3)]2的結構與DFT理論計算軌域圖----------------------------------------------------------------------------------------------p. 18
圖1-20. Fe2[PhenylNCHNPhenyl]3的結構與其軌域交互作用圖-------------------p. 19
圖1-21. Co2[PhenylNCHNPhenyl]3的結構與其軌域交互作用圖------------------p. 19
方程式2-1. 還原Cr2(□-Cl)2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2(THF)2 1-----p. 21
圖2-1. 3在0.2 M的TBAP的四氫呋喃溶劑中的循環伏譜圖。掃描速度為0.05 V/s -------------------------------------------------------------------------------------------------p. 22
方程式2-2. 還原Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3----------------------p. 22
方程式2-3. 還原Cr2(□-Cl)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]¬2(THF)2 6------------------------------------------------------------------------------------------------p. 23
方程式2-4. 從CrCl2[ArNCRNAr](THF)2到Cr2[ArNCRNAr]2的反應過程------p. 24
方程式2-5. 第三丁基鋰與Cr2(□-Cl)[ (o-ClC6H4)NCHN(o-ClC6H4)]3 15反應--p. 25
圖2-2. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3的分子結構圖及重要鍵長 (Å)和鍵角 (°)------------------------------------------------------------------------------------p. 26
圖2-3. 3的77 K EPR光譜-----------------------------------------------------------------p. 27
圖2-4. [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4的分子結構圖及重要鍵長 (Å)和鍵角 (°)---------------------------------------------------------p. 28
圖2-5. Cr2(□-Cl)2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2(THF)2 6的分子結構圖以及重要鍵長 (Å)和鍵角 (°)------------------------------------------------------------p. 30
圖2-6. CrCl2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)](THF)2 11的分子結構圖及重要鍵長 (Å)和鍵角 (°)------------------------------------------------------------------------p. 32
圖2-7. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2THF 2a的分子結構圖及重要鍵長 (Å)和鍵角 (°)---------------------------------------------------------------------------p. 33
圖2-8. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ 2-methylTHF 2b的分子結構圖及重要鍵長 (Å)和鍵角 (°)---------------------------------------------------------------p. 34
圖2-9. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 ∙ □-□4-C7H8 2c的分子結構圖及重要鍵長 (Å)和鍵角 (°)---------------------------------------------------------------------p. 36
圖2-10. 2c上的甲苯之碳-碳鍵長示意圖-----------------------------------------------p. 37
圖2-11. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 8的分子結構圖及重要鍵長 (Å)和鍵角 (°)--------------------------------------------------------------------------------p. 38
圖2-12. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 ∙ 2THF 10a的分子結構圖及重要鍵長 (Å)和鍵角 (°)------------------------------------------------------------------------p. 39
圖2-13. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 ∙ 2THF 10b的分子結構圖及重要鍵長 (Å)和鍵角 (°)------------------------------------------------------------------------p. 41
圖2-14. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12的分子結構圖及重要鍵長 (Å)和鍵角 (°)--------------------------------------------------------------------------------p. 42
圖2-15. Cr2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)]2 14的分子結構圖及重要鍵長 (Å)和鍵角 (°)---------------------------------------------------------------------------p. 43
圖2-16. 橋接v.s.螯合----------------------------------------------------------------------p. 43
表2-1. 重要鍵長鍵角比較----------------------------------------------------------------p. 44
圖2-17. Cr2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]Li}2{μ-[(o-ClC6H4)NCH(tBu)N(o-ClC6H4)]} 16的分子結構圖及重要鍵長 (Å)和鍵角 (°)--------------------------------------p. 46
圖2-18. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3 3的UV-vis光譜圖(以四氫呋喃為溶劑)---------------------------------------------------------------------------------------p. 48
圖2-19 [K(cryptand [2.2.2])]{Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]3} 4的UV-vis光譜圖(以四氫呋喃當溶劑)--------------------------------------------------------------p. 48
圖2-20. Cr2[(2,6-Me2C6H3)NCHN(2,6-Me2C6H3)]2 2 的UV-vis光譜圖(以四氫呋喃當溶劑)---------------------------------------------------------------------------------------p. 50
圖2-21. Cr2[(2,4,6-Me3C6H2)NCHN(2,4,6-Me3C6H2)]2 8的UV-vis光譜圖 (以正己烷當溶劑)------------------------------------------------------------------------------------p. 50
圖2-22. Cr2[(2,6-Et2C6H3)NCHN(2,6-Et2C6H3)]2 10的UV-vis光譜圖 (以正己烷當溶劑)------------------------------------------------------------------------------------------p. 51
圖2-23. Cr2[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2 12的UV-vis光譜圖(以四氫呋喃當溶劑)------------------------------------------------------------------------------------p. 51
圖2-24. Cr2[(2,6-i-Pr2C6H3)NC(CH3)N(2,6-i-Pr2C6H3)]2 14 的UV-vis光譜圖(以四氫呋喃當溶劑)------------------------------------------------------------------------------p. 52
圖2-25. 3的DFT理論計算----------------------------------------------------------------p. 53
圖2-26. Jahn-Teller Effect of M2L6-------------------------------------------------------p. 54
圖2-27. 4的DFT理論計算----------------------------------------------------------------p. 54
圖2-28. 12的DFT理論計算--------------------------------------------------------------p. 55
圖2-29. V[(2,6-i-Pr2C6H3)NCHN(2,6-i-Pr2C6H3)]2(THF)的分子結構圖及重要鍵長 (Å)和鍵角 (°)--------------------------------------------------------------------------------p. 56
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