含多芽氮配位基與d10過渡金屬配位化合物之合成與結構探討

Synthesis and structural characterization of d10 metal complexes containing polydentate nitrogen ligands

胡慧玲(Hui-Ling Hu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/博士(2015年)

https://doi.org/10.6840/cycu201500048

摘要

本論文主要討論多芽氮配位基與d10過渡金屬鹽類反應所形成之化合物結構，並探討分子間作用力，包含了兩部分。
第一部分
以四種含有雙醯胺吡啶官能基的配位基N,N′-di(pyridin-2-yl)oxalamide (L1)；N,N′-di(pyridin-2-yl)succinamide (L2)； N,N′- di(pyridin-3-yl)oxalamide (L3)與 N,N′- di(pyridin-2-yl)adipamide (L4)，分別與Ag(I)，Cd(II) ，Hg(II)與Zn(II)金屬鹽類進行反應，可得到雙核錯合物[Ag2(L1)(CH3CN)6](SbF6)2, 1，Ag2(L1)(CH3CN)2(CF3CO2)2, 2與Ag2(L1)(CH3CN)2(p-TsO)2, 3, (p-TsO- = p-toluenesulfonate anion)，Hg2(L1)(NO3)2, 15，Hg2I4(L3)2, 19，Hg2Br4(L4), 21與Hg2I4(L4), 22，一維鏈狀高分子 [Ag(L1)(CH3CN)(CF3SO3)]n, 4， {[Ag2(L2)2(p-TsO)](p-TsO)•2CH3CN}n, 5，{[Ag(L2)](SbF6)•CH3CN}n, 6，{[Ag(L3)](SbF6)•DMF}n, 7，{[Ag(L3)](PF6)}n, 8，{[Ag(L4)](BF4)•CH3CN}n, 9，{[Ag(L4)](PF6)}n, 10，{[Ag(L4)](SbF6)•CH3CN}n, 11，{[Cd(L1)(H2O)2](ClO2)2•(CH3)2CO}n, 12，[HgCl2(L1)]n, 13，[HgBr2(L1)]n, 14，[ZnBr2(L3)•DMF]n, 16，[ZnI2(L3)•DMF]n, 17，[HgBr2(L3)•DMF]n, 18與 [Cd(L4)(ClO4)2]n, 20。以上所有化合物均經元素分析儀、IR光譜儀分析鑑定，並利用單晶X繞射儀鑑定其結構。
化合物1 - 5分子間藉由多種氫鍵及π-π stacking與Ag---O等多種弱作用力形成二維超分子結構；其中化合物4利用一維高分子鏈間氫鍵形成一維階梯鏈狀超分子結構。化合物6則藉由各種氫鍵及Ag---O等弱作用力形成三維超分子結構。一維鏈狀高分子錯合物7與8透過未配位的陰離子或是共結晶的溶劑利用Ag---F或Ag---O作用力與金屬相連，分子間透過氫鍵、作用力相互連結分別形成二維層狀超分子結構與三維網狀超分子結構。一維鋸齒鏈狀高分子錯合物9 - 11，均利用配位基橋接銀原子；分子間藉由多種氫鍵及π-π stacking與Ag---O等多種弱作用力形成三維超分子結構。一維螺旋鏈狀高分子錯合物12為配位基利用螯合的方式形成一維螺旋高分子鏈狀結構，鏈狀結構間透過π – π stacking與N-H---O及C-H---O氫鍵相互連結形成三維網狀超分子結構。化合物13乃為分子間透過芳香環間作用力及氫鍵而堆疊形成三維網狀超分子；化合物14則透過氫鍵形成二維層狀結構。化合物15是一個新型雙核錯合物，兩個雙核汞分子間透過點對面形式的芳香環之間的作用力及氫鍵，形成三維立體網狀的超分子結構。在化合物16 - 18中，一維鏈狀高分子間與共結晶的溶劑分子間藉由氫鍵相連；雙核金屬環型分子19則是透過π – π stacking與氫鍵相互連結，形成三維網狀超分子結構。化合物20利用螯合的方式形成一維高分子鏈狀結構，鏈狀結構間氫鍵相互連結形成三維網狀超分子結構。化合物21的分子間以各種作用力及氫鍵形成三維網狀超分子；化合物22的分子間則透過弱作用力及氫鍵形成二維層狀結構。

第二部分
以含胺基嘧啶配位基2,4,6-triaminopyrimidine (L5)與2-amino-4-methoxy-6-methylpyrimidine (L6)分別與含銀之金屬鹽類進行反應，可得一維鏈狀高分子錯合物{[Ag2(L5)2(ClO4)](ClO4) • CH3OH}n, 23與{[Ag(L5)](p-TsO) • CH3OH}n, 24，以及新型四核銀的金屬環型結構分子[Ag4(L5)4(p-TsO)2](p-TsO)2 • 6DMF, 25，一維鏈狀高分子錯合物{[Ag2(L6)2(SO4)]•6H2O}n, 26，{[Ag(L6)](BF4)}n, 27， [Ag(L6)(CF3CO2)]n, 30， {[Ag(L6)](CF3SO3)}n, 31，二維菱格網狀結構的{[Ag(L6)2](PF6)}n, 29，與零維單核銀分子錯合物[Ag(L6)2](ClO4), 28。上述所有化合物已經元素分析儀、IR光譜儀分析鑑定，並利用單晶X繞射儀鑑定其結構。
化合物23 – 25均以含胺基嘧啶配位基L5橋接銀原子在不同的CH3OH與DMF溶劑或陰離子作用下形成多核分子，其中的化合物25呈現為零維的四核銀金屬環型結構；分子間藉由多種氫鍵及C-H---π，π – π stacking與Ag---O等多種弱作用力堆疊形成多維超分子結構。以L6與Ag(I)金屬鹽類反應獲得一維鏈狀高分子化合物26 – 27與 30 - 31的分子間透過π – π stacking芳香環間作用力與其他弱作用力及氫鍵形成三維網狀超分子；化合物28利用單芽配位的方式形成零維單核結構，結構間透過各種弱作用力與氫鍵相互連結形成三維網狀超分子結構；二維菱格網狀化合物29的分子間則藉由氫鍵形成三維網狀超分子結構。

關鍵字

d10過渡金屬化合物 ； 配位高分子

並列摘要

This thesis includes two parts discussing the synthese, structures and interactions of d10 metal complexes containing polydentate nitrogen ligands.

Part I.
The reactions of N,N′-di(pyridin-2-yl)oxalamide (L1), N,N′-di(pyridin-2-yl)succinamide (L2), N,N′- di(pyridin-3-yl)oxalamide (L3) and N,N′- di(pyridin-2-yl)adipamide (L4) with Ag(I) , Cd(II) , Hg(II) and Zn(II) metal salts afforded dinuclear and one-dimensional complexes, which have been fully characterized by EA and IR analysis and single-crystal X-ray diffraction.
The dinuclear complexes [Ag2(L1)(CH3CN)6](SbF6)2, 1, Ag2(L1)(CH3CN)2(CF3CO2)2, 2, and Ag2(L1)(CH3CN)2(p-TsO)2, 3, (p-TsO- = p-toluenesulfonate), and 1-D polymeric chains [Ag(L1)(CH3CN)(CF3SO3)]n, 4, {[Ag2(L2)2(p-TsO)](p-TsO) • 2CH3CN}n, 5, {[Ag(L2)](SbF6) • CH3CN}n, 6, {[Ag(L3)](SbF6)•DMF}n, 7, {[Ag(L3)](PF6)}n, 8, {[Ag(L4)](BF4) • CH3CN}n, 9, {[Ag(L4)](PF6)}n, 10, and {[Ag(L4)](SbF6) • CH3CN}n, 11 form supermolecular structures through π-π stacking and weak Ag---O or Ag---F interactions. The 1-D helical chains of {[Cd(L1)(H2O)2](ClO2)2 • (CH3)CO}n, 12, are linked through π – π stacking interactions and N-H---O及C-H---O hydrogen bonds to form a 3-D supramolecular framework, and those of [HgCl2(L1)]n, 13, [HgBr2(L1)]n, 14, and the dinuclear Hg2(L1)(NO3)2, 15, are interlinked through π – π stacking interactions and various hydrogen bonds. The 1-D polymeric chains of [ZnBr2(L3) • DMF]n, 16, [ZnI2(L3) • DMF]n, 17 and [HgBr2(L3) • DMF]n, 18, are linked by their DMF molecules through the hydrogen bonds, while the molecules of the dinuclear Hg2I4(L3)2, 19 interact each with other through π – π stacking interactions and hydrogen bonds to form 3-D supramolecular frameworks. Similarily, the 1-D chains [Cd(L4)(ClO4)2]n, 20, and the dinuclear complexes, Hg2Br4(L4), 21 and Hg2I4(L4), 22 form 3-D nets through π – π stacking interactions and various hydrogen bonds.

Part II.
The amino-pyrimidine ligands, 2,4,6-triaminopyrimidine (L5) and 2-amino-4-methoxy-6-methylpyrimidine (L6) reacted with Ag(I) metal salts to form the complexes {[Ag2(L5)2(ClO4)](ClO4) • CH3OH}n, 23, {[Ag(L5)](p-TsO) • CH3OH}n, 24, [Ag4(L5)4(p-TsO)2](p-TsO)2 • 6DMF, 25, {[Ag2(L6)2(SO4)]•6H2O}n, 26,{[Ag(L6)](BF4)}n, 27, [Ag(L6)2](ClO4), 28, {[Ag(L6)2](PF6)}n, 29, [Ag(L6)(CF3CO2)]n, 30, and {[Ag(L6)](CF3SO3)}n, 31. All compounds have been characterized by spectroscopic methods and their structures determined by X-ray crystallography.
The Ag(I) atoms of 23 and 24 are bridged by the L5 ligands to form 1-D polymeric infinite chain structures, and 0-D tetranuclear complex. The molecules of 23 – 25 are interlinked through weak C-H---π, π – π stacking and Ag---O interactions. The 1-D chains 26, 27, 30 and 31, and the molecules of the 0-D of 28 and 2-D grids of 29, are interlink through π – π stacking interactions and hydrogen bonds to form 3-D frameworks.

並列關鍵字

coordination polymer ； d10 metal ions

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