含三醯胺吡啶、硫醇和氮雜-18-冠醚-6二硫代甲酸配位基超分子配位化合物的設計、合成和自我組裝

Design, Synthesis and Self-Assembly of Supramolecular Coordination Compounds Containing Tripyridylamide, Thiolate and (Aza-18-crown-6)dithiocarbamate Ligands

晁安(Chao, An)

指導教授 ： 曾炳墝

國立中正大學/理學院/化學暨生物化學系/碩士(2012年)

摘要

本論文主題為「含三醯胺吡啶、硫醇和氮雜-18-冠醚-6二硫代甲酸配位基超分子配位化合物的設計、合成和自我組裝」，主要分成三個部分。
第一部分為有機－無機配位高分子的研究。利用含吡啶醯胺(pyridylamide)官能基，且具有C3對稱性的三芽配位基N,N’,N’’-tris(4-(4-pyridylamide)phenyl)amine (L20)，分別與CuI、CuSCN、Zn(ClO4)2和Cd(ClO4)2進行反應，合成出一系列稀有的二維巨輪烷(polyrotaxane)化合物，經X光單晶繞射技術確定其固態結構如下，{[(Cu2I2)(μ2-L20)2](DMF)4(MeOH)2}n (1)、{[Cu(μ2-L20)2(SCN)2](DMF)3}n (2)、{[Zn(μ2-L20)2(ClO4)2](EtOH)4}n (3)和{[Cd(μ2-L20)2(ClO4)2](EtOH)4}n (4)。特別的是，L20在四個化合物中皆只有雙芽配位，而另一個吡啶官能基則完全沒有參與配位，成為一維的雙鋸齒狀(double-zigzag)結構，一維鏈與鏈之間再進而互穿形成二維的巨輪烷結構。化合物1 - 4的結構大致上皆類似，其中化合物2的中心金屬在此被氧化成二價銅，並且也用電子自旋共振(electron paramagnetic resonance)做順磁性鑑定。
第二部分的研究則是以錸化合物Re2(CO)10為起始物，分別與2-mercaptobenzothiazole (HNS2)、2-mercaptobenzimidazole (H2N2S)、2-mercaptobenzoxazole (HNOS)和trithiocyanuric acid (H3N3S3)利用溶劑熱法一鍋化(one-pot)反應，自我組裝(self-assembly)得到一系列含有fac-(CO)3Re的超分子。這些硫醇配位基在溶劑熱法(solvothermal)反應條件下容易發生C-S鍵的斷裂和S-S鍵的生成，使配位基重組，利用X光單晶繞射和元素分析來鑑定其中in-situ配位基的結構和錸化合物的組成。我們也嘗試利用X光粉末繞射和紅外線光譜來鑑定在不同溫度或不同溶劑下的產物，其中以HNS2為起始物，在不同條件下分別得到了cis-(Re(CO)3)2(NS2)2 (5)、trans-(Re(CO)3)2(SNS2)2 (6)和(Re(CO)3)2(NSNS2)2 (7)三個完全不同的產物。而H2N2S和HNOS則分別得到cis-(Re(CO)3)2(HN2N2S)2 (8)和cis-(Re(CO)3)2(SNOS)2 (9)。另外，以H3S3N3為起始物，並沒有觀察到新的in-situ配位基生成，但在不同反應濃度下分別得到的六核的六角柱狀分子(Re(CO)3)6(S3N3)2 (10)，及其三核的中間體(Re(CO)4)3(S3N3) (11)，再利用11與bpy (4,4’-bipyridine)反應可以進一步得到六角柱形的籠狀(cage-like)分子(Re(CO)3)6(bpy)3(S3N3)2 (12)。
最後，第三部分為含二硫代甲酸(dithiocarbamate)配位基(aza-18-crown-6)dithiocarbamate (C18N1-CS2)與一價、二價銅的配位化學和一價金化合物親金性(aurophilicity)的研究，並利用X光單晶繞射技術確定其固態結構。當C18N1-CS2與CuI溶於乙腈反應後，發現部分一價銅被氧化成二價銅，同時得到具有混價金屬的一維鏈狀聚合物[Cu(Cu4Na2I6)(C18N1-CS2)2]n (13)和單體Cu(C18N1-CS2)2 (14)。當我們以CuBr2為起始物反應時，在乙腈溶液中雖然電灑質譜儀(ESI-MS)偵測到14的訊號，但在固態結構鑑定卻得到化合物CuNa(H2O)(C18N1-CS2) (15)。最後，以CuSO4為起始物則可以單純得到14，並且以X光粉末繞射和元素分析鑑定其各個晶相和成分。另外，我們也合成出雙核的化合物Au2(C18N1-CS2)2 (16)，並且分子間藉由金…金作用力形成一維直鏈結構。有趣的是16有蒸氣變色(vaporochromic)的行為，利用固態螢光光譜、X光粉末繞射和氫核磁共振(1H NMR)的偵測下發現到隨著空間中的乙腈分子蒸散，晶相以及螢光也會隨之改變。特別的是，在我們滴入各種不同溶劑，觀察其螢光的改變，發現當滴入苯的溶劑時，會使發光強度約增強二十倍。遠遠超過其他溶劑，所以對苯的辨識力超過其他溶劑。最後，我們以第三丁基苯(tert-butylbenzene)成功置換化合物16結構中的乙腈分子，完成單晶到單晶的轉換(single-crystal-to-single-crystal transformation)，並且從固態結構中發現，分子間金…金距離可能為影響螢光行為的關鍵。

關鍵字

超分子 ； 自組裝 ； 巨輪烷 ； 溶劑熱法 ； 籠狀分子 ； 親金性 ； 醯胺吡啶 ； 硫醇 ； 二硫代甲酸 ； 蒸氣變色

並列摘要

This thesis entitled “syntheses, structures and luminescent properties of supramolecular coordination compounds containing tripyridylamide, thiolate and (aza-18-crown-6)dithiocarbamate ligands” includes three parts. In the first part, the tripyridylamide ligand N,N’,N’’-tris(4-(4-pyridylamide)phenyl)amine (L20) with a C3 symmtry has been designed and synthesized. The reactions of CuI, CuSCN, Zn(ClO4)2 and Cd(ClO4)2 with L20 produced compounds {[(Cu2I2)(μ2-L20)2](DMF)4(MeOH)2}n (1), {[Cu(μ2-L20)2(SCN)2](DMF)3}n (2), {[Zn(μ2-L20)2(ClO4)2](EtOH)4}n (3) and {[Cd(μ2-L20)2(ClO4)2](EtOH)4}n (4), respectively. All compounds have been characterized by EA, IR, TGA and PXRD and their structures have been also determined by X-ray crystallography, confirming that 1 – 4 are two-dimensional polyrotaxane networks. Interestingly, compound 2 shows that Cu(I) ion was oxidized to Cu(II) ion, which was also indentified by an EPR spectroscopic method.
In the second part, couple of new compounds have been successfully synthesized by solvothermal reactions of Re2(CO)10 with 2-mercaptobenzothiazole (HNS2), 2-mercaptobenzimidazole (H2N2S), 2-mercaptobenzoxazole (HNOS) and trithiocyanuric acid (H3N3S3) in different solution or temperature systems. These thiolate ligands in solvothermal conditions could undergo in situ cleavage and formation of C-S or S-S, C-N bonds, respectively. When HNS2 acts as a precursor, the reaction products in different temperature or solvent condition was obtained by cis-(Re(CO)3)2(NS2)2 (5), trans-(Re(CO)3)2(SNS2)2 (6) and Re(CO)3(NSNS2)2(SH) (7). While HN2S and HNOS was used as precursors, cis-(Re(CO)3)2(HN2N2S)2 (8) and cis-(Re(CO)3)2(SNOS)2 (9) was obtained, respectively. In addition, the precursor H3N3S3 was used in different concentrations of reations, hexanuclear cluster (Re(CO)3)6(S3N3)2 (10) and its intermediate (Re(CO)4)3(S3N3) (11) were isolated and characterized. Finally, 11 was reacted with bpy (4,4’-bipyridine) to give a moleculer cage (Re(CO)3)6(bpy)3(S3N3)2 (12). All compounds have been characterized by EA, IR and PXRD and their structures have been determined by single-crystal X-ray diffraction.
In the third part, the ligand (aza-18-crown-6)dithiocarbamate (C18N1-CS2) was reacted with CuI, CuSO4 and CuBr2 to obeain [Cu(Cu4Na2I6)(C18N1-CS2)2]n (13), Cu(C18N1-CS2)2 (14) and CuNa(H2O)(C18N1-CS2) (15) in solid state, respectively. These compounds have been identified characterized single-crystal X-ray diffraction and then XPS and EPR date to identify them. Additionally, we synthesized a dinuclear gold(I) dithiocarbamate compound, Au2(C18N1-CS2)2, (16), by reacting Au(Me2S)Cl with C18N1-CS2 in acetonitrile. Single-crystal diffraction shows the formation of a linear Au•••Au chain with intra- and intermolecular Au•••Au distances of 2.7249(3) and 2.8355(3) Å, respectively. To investigate the correlation between the luminescence and solvent guests, we set out to examine the effect of acetonitrile molecules in the structure on solid-state luminescence, examined by powder X-ray diffraction and 1H NMR spectroscopy. Interestingly, the vapochromic behavior toward some organic vapors can be found. Finally, solvent induced single-crystal-to-single-crystal transformation from acetonitrile to tert-butylbenzene has been accomplished.

並列關鍵字

self-assembly ； supramolecular ； polyrotaxane ； one-pot ； in-situ ； solvothermal ； vaporochromic ； single-crystal-to-single-crystal transformation ； aurophilicity ； mechanochromic ； dithiocarbamate ； pyridylamide ； thiolate ； Re2(CO)10

參考文獻

1. Lehn, J. M. Pure Appl. Chem. 1978, 50, 871.

2. Pedersen, C. J. Angew. Chem. Int. Ed. Engl. 1988, 27, 1021.

3. Lehn, J. M. Angew. Chem. Int. Ed. Engl. 1988, 27, 90.

4. Cram, D. J. Angew. Chem. Int. Ed. Engl. 1988, 27, 1009.

7. Prior, T. J.; Rosseinsky, M. J. J. Chem. Soc. Chem. Comm. 2001, 1222.