双吡唑论文：双吡唑超分子化学

双吡唑论文：双吡唑银铜自组装超分子化学
【中文摘要】在本论文的研究中,我们共合成了3个未见报道的半刚性双吡唑配体和它们与铜(Ⅰ)、铜(Ⅱ)、银(Ⅰ)和镉(Ⅱ)形成的6个配合物,并用元素分析、红外光谱、核磁共振、质谱和X-射线衍射等手段对这些化合物进行了表征。

本文中用到的3个有机配体如下：1.4,4’-(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二苯基吡唑(H2L1)；2.4,4’-(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二甲基吡唑(H2L2)；3.4,4’-(2,7-二亚甲基萘撑)-二-3,5-二苯基吡唑(H2L3)；6个配合物的分子式如下：{ (BF4)}n (1) (BF4)2-2H2O (2) {(NO3)}n (3) n (4) ·11H20 (5) 4H2O (6)它们的结构可以分为以下三类：1.双核配合物：(BF4)2·2H2O (2)和·11H2O (5)为0维的双核配合物,其中2是一个M2L2型的矩形配合物；配合物3是一个
M2L4型笼状结构,其中的铜(Ⅱ)原子均为五配位。

2.六核配合物：Cu6(L3)3·4H2O (6)为0维的六核三棱柱状超分子笼,此结构中配体H2L3上N-H质子成功脱去,笼子的上下两面是Cu3N6的九元环,侧棱是三个萘环支撑,萘环平面和九元环平面接近垂直。

3.一维配位聚合物：{ (BF4)}n (1).{(NO3)}n (3)和n (4)均为一维链状结构。

其中配合物1中配体H2L1呈反式构象,而结构中的pi-pi堆积作用使这种反式构象更加稳定；配合物3中,配体H2L2为顺式构象,金属与配体交替形成墙垛形链状结构；配合物4中,配体H2L2同样为反式构象,
金属与配体交替形成Z字型一维链,每个金属上有两个Γ配位作为链的装饰。

通过对以上结构的研究,我们得出以下结论：1.双吡唑配体中,吡唑环3,5位的取代基对配体在结构组装中表现出来的顺反构象影响很大。

比较配体H2L1和H2L2我们可以看出,由于前者中存在C-H-π而且组装的结构中存在pi-pi堆积,导致其很难在常温条件下与金属离子以顺式构象进行组装；配体H2L2中我们用甲基取代了苯基,
这个问题得到了解决,在其组装体中,顺式构象更为常见。

2.双吡唑脱去质子,配位点增加一倍,这在很大程度上使组装体的复杂性提高,可以预期得到更有趣的晶体结构。

然而此类配体脱质子后易形成难溶的配合物粉末,使得进一步的结构确定十分困难。

我们尝试了在水热条件下进行分子组装并取得了很好的效果(配合物6)
【英文摘要】In this paper, three unprecedented semi-rigid bipyrazolyl ligands and their six complexes with Cu(Ⅰ)、
Cu(Ⅱ)、Ag(Ⅰ)和Cd(Ⅱ) were synthesized, and characterized with element analyses, IR spectra, HNMR, MS and X-ray diffraction.The three ligands are: 4,4’
-(2,3,5,6-tetramethyl-1,4-dimethylenephenyl)-
3,5-diphenylbipyrazole (H2L1) 4,4’
-(2,3,5,6-tetramethyl-1,4-dimethylenephenyl)-
3,5-dimethylbipyrazole (H2L2) 4,4’
-(2,7-naphthalenediylbis(methylene))-bis(3,5-diphenylbipyra zole) (H2L3)The six complexes are: {[Ag(H2L1)] (BF4)}n (1)
[Ag2(H2L2)2](BF4)2·2H2O (2) {[Ag(H2L2)](NO3)}n (3)
[Cd(H2L2(I)2]n (4) [Cu2(H2L2)4(SO4)2]·11H2O (5)
[Cu6(L3)3]·4H2O (6)The complexes are divided into three categeries according to the styles ofcoordination:1. Dinuclear complexes: [Ag2(H2L2)2](BF4)2·2H2O (2) and
[Cu2(H2L-)4(SO4)2]·11H2O (5) are OD dinuclear complexes. In which, the former adopts a discrete rectangular structure, and the later exhibits a discrete cage structure. The Ag(I) atoms are linear two-coordinated and the Cu(II) atoms are
five-coordinated.2. Hexanuclear complex:[Cu6(L3)3]-4H2O (6) adopts an OD hexanuclear cage-like structure.In the structure, the pyrazolyl rings are deprotonated clearly, and the top and bottom of the cage are two nine-membered rings composite of three Cu(Ⅰ) atoms and six N atoms. The two nine-membered rings are connected with three naphthyl rings.3. ID
complexes:{[Ag(H2L’)](BF4)}n (1),{[Ag(H2L2)](NO3)}n (3) and [Cd(H2L2)(Ⅰ)2]n (4) are all 1-D complexes. Ligand H2L1 adopts a trans-conformation in complex 1, and the pi-pi interaction consolidates the conformation. In complex 3, ligand H2L2 is in cis-conformation, alternate with Ag(Ⅰ) atoms to form a 1-D chain. A zigzag chain structure is found in complex 4, in which each Cd(Ⅱ) atom has two I- coordinated as
accessories.Conclusions can be drawn from this study:1. The substituent groups on 3,5 positions play a great role in
self-assembly for bipyrazolyl ligands to adopt different conformation. Comparing with the ligand H2L2, H2L1 has C-H
πinteraction in the free molecular and pi-pi stacking interaction in the self-assembly, which result in the difficulty to perform cis-conformation in the self-assembly with metal ions. When we use methyl group instead of the phenyl group, this problem is tackled.2. The tough thing in the
self-assembly with bipyrazolyl ligands and metal ions is deprotonation. The deprotonated ligands can offer more coordination sites, and will make big contribution in the complication of the structures. However, experience indicates that in this semi-rigid bipyrazolyl system, it is difficult to be successful in deprotonation and obtaining crystals with proper size at the same time. Hence, we tried to solve this problem in hydrothermal condition, and be successful.
【关键词】双吡唑银铜自组装超分子化学
【英文关键词】bipyrazole silver copper self-assembly supermolecular
【目录】金属/双吡唑配合物的合成、结构与性质研究摘要4-6Abstract6-7第一章前言10-20 1.1 超分子化学的研究现状10-11 1.2 吡唑化学的发展11-19 1.3 选题意义19-20第二章实验部分20-26 2.1 试剂和仪器20 2.2 配
体的合成20-23 2.2.1 4,4’-(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二苯基吡唑的制备21 2.2.2 4,4’-(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二甲基吡唑的制备21-22 2.2.3 4,4’-(2,7-二亚甲基荼撑)-二-3,5-二苯基吡唑的制备22-23 2.3 配合物的合成23-25 2.3.1 配合物{[Ag(H_2L~1)](BF_4)}_n的合成23 2.3.2 配合物[Ag_2(H_2L~2)_2](BF_4)_2·2H_2O的合成23-24 2.3.3 配合物{[Ag(H_2L~2)](NO_2)}_n的合成24 2.3.4 配合物[Cd(H_2L~2)(I)_2]_n的合成24 2.3.5 配合物[Cu_2(H_2L~2)_4(SO_4)_2]·11H_2O的合成24 2.3.6 配合物Cu_6(L~3)_3·4H_2O的合成24-25 2.4 X-射线衍射数据收集25-26第三章结果与讨论26-43 3.1 结构与表征26-39 3.1.1 4,4’(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二苯基吡唑的结构26-29 3.1.2 4,4’-(2,3,5,6-四甲基-1,4-二亚甲基苯撑)-二-3,5-二甲基吡唑的结构29-30 3.1.3 配体4,4’-(2,7-二亚甲基萘撑)-二-3,5-二苯基吡唑的结构30-31 3.1.4 配合物{[Ag(H_2L~1)](BF_4)}_n(1)的结构31-32 3.1.5 配合物[Ag_2(H_2L~2)_2](BF_4)_2·2H_2O(2)的结构32-34 3.1.6 配合物{[Ag(H_2L~2)](NO_3)}_n(3)的结构34 3.1.7 配合物[Cd(H_2L~2)(I)_2]_n(4)的结构34-36 3.1.8 配合物[Cu_2(H_2L~2)_4(SO_4)_2]·11H_2O(5)的结构36 3.1.9 配合物Cu_6(L~3)_3·4H_2O(6)的结构36-39 3.2 性质与表征39-40 3.3 结论与展望40-43 3.3.1 结论40-42 3.3.2 展望42-43参考文献43-47发表文章47-48致谢48【索购全文找】1.3.9.9.3.8.8.4.81.3.8.1.1.3.7.2.1
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