含多芽配位基金屬錯合物之晶體工程

Crystal Engineering of Metal Complexes Containing Multidentate Ligands

葉俊葳(CHUN-WEI YEH)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/博士(2008年)

https://doi.org/10.6840/cycu200900660

摘要

本論文主要討論多芽配位基與過渡金屬鹽類所形成之化合物結構，並
探討分子間的之作用力，包含了四個部份。
第一部分
兩種新型含有雙醯胺吡啶官能基的配位基，
N,N'-(methylenedi-p-phenylene)bis(pyridine-4-carboxamide) (L1) 與
N,N'-(methylenedi-p-phenylene)bis(pyridine-3-carboxamide) (L2)已經被合成
出來。以L1配位基與CuX2或Ag2SO4鹽類在DMF / H2O溶液中反應，可分別
得到化合物[CuX2(L1)2]∞ (X = F, 1, X = Cl, 2 及X = Br, 3) ，
{[Cu(DMF)(L1)2](X)2}∞ (X = NO3, 4, X = ClO4, 5及X = BF4, 6) 與
{[Ag(L1)2](SO4)}∞, 7，當Cu(NO3)2 ⋅ 3 H2O與配位基L2在CH3OH / DMSO中反
應，可得到化合物{[Cu(L2)(DMSO)2(NO3)](NO3)}∞, 8。以上所有化合物均利
用元素分析儀、IR光譜儀與熱重分析儀分析鑑定之，化合物2、3、4、7與8
的結構則是利用單晶X-ray繞射儀鑑定，並確定化合物2、3、4、7與8皆為
一維配位高分子。
錯合物2、3 與4 為一維圈狀鏈結構，由奈米尺寸之M2L2 菱形分子格
組成，其菱格大小在化合物2、3、4 中分別為16.95 × 19.13、17.03 × 19.06
與16.66 × 19.94 Å2。錯合物2 - 4 結構中，一維鏈間透過C-H---X (X = Cl, Br
與O)及N-H---X 多種氫鍵形成三維的超分子結構。錯合物7 為一維鋸齒鏈
狀配位高分子，鏈與鏈之間透過Ag---O 作用力連結並組成一維梯狀結構。
化合物8 中，一維正弦波型鏈之間透過C-H---O 與N-H---O 多種氫鍵，與
芳香環間的π – π 作用力相互連結形成三維的超分子結構。
第二部分
利用2,3-diphenylquinoxailne (L3)配位基與多種過渡金屬鹽類在不同溶
劑系統下反應，可得到多種的新型的零維、一維及二維超分子化合物。所
有錯合物均利用元素分析儀、IR光譜儀與單晶X-ray繞射儀鑑定之。
錯合物[Ag(L3)2](X) (X = ClO4, 9; X = PF6, 10;與X = SbF6, 11)是單核的
結構，彼此透過多種分子間的C-H---Ag 與Ag---X (X = O or F)作用力或
C-H---X 氫鍵，相互連結形成三維超分子結構。錯合物{[Ag(L3)(L’)][X]}∞, (X
= BF4, L’ = H2O, 12; X = BF4, L’ = MeCN, 13 與X = ClO4, L’ = MeCN, 14)，
[Ag(L3)(CF3SO3) · H2O]∞, 15 · H2O 與{[Ag(L3)][SbF6] · 0.5CH2Cl2}∞, 16 ·
0.5CH2Cl2 是一維配位高分子鏈狀結構，彼此透過分子間的anion---π 作用力
與C-H---X(X = O 或F)氫鍵相互連結。錯合物14 中的過氯酸根陰離子利用
三芽的形式與配位基L3 的芳香環作用，並藉此形成少見的分子內[ClO4-π]n
鋸齒鏈狀結構。雙核金屬錯合物Ag2(L3)(NO3)2(DMF)2, 17 則是透過分子間
的π – π 作用力、Ag---O 弱作用力以及C-H---O 形式的氫鍵相互連結形成一
維梯狀的超分子鏈狀結構。錯合物[Ag2(L3)(NO3)2(L’)2]∞ (L’ = H2O, 18 與L’
= MeCN, 19)，透過其構築單元[Ag2(L3)]2+與水分子或是硝酸根陰離子橋接
進行連結，形成一維梯狀配位高分子鏈狀結構。錯合物[Ag2(L3)(NO3)2]∞, 20
則是二維縐摺狀六角形網狀結構，其結構是透過兩組一維配位高分子鏈狀
結構-[Ag-L3-Ag-(μ2-O-NO3)]-與-[Ag-(μ1-O, μ1-O’-NO3)-Ag-(μ2-O-NO3)]-相
互交織而成。錯合物[Ag(L3)(p-TsO)]∞, 21 是二維的縐摺格子層狀結構，其
是由-[Ag-L3]-與-[Ag-(μ1-O, μ1-O’-p-TsO)]-兩種一維鏈所組成。錯合物
[CuI(L3)]2, 22 是一個雙核金屬分子，中心金屬銅(I)透過兩個碘原子橋接並
透過與配位基L3 的單芽氮鍵結形成三配位的形成[Cu2I2]的雙核中心。一系
列的單核錯合物CuX2(L3)2, (X = Cl, 23 及X = Br, 24)與HgX2(L3)2, (X = Cl,
25 與X = Br, 26)其分子間透過C-H---X (X = Cl 或Br)氫鍵與π – π 作用力形
成二維的層狀超分子結構。
值得注意地，在錯合物9 - 21 之中，藉由單晶X-ray 的結構鑑定，配位
基L3 上的喹唑啉官能基上的氫原子與銀原子之間的距離在凡德瓦作用力
半徑之內，而發現其有C-H---Ag 的分子內弱作用力存在。在本研究中亦發
現，含有配位基L3 多種形式的一價銀錯合物的結構，會因為陰離子、溶劑
及金屬與配位基的比例等多種變因而改變。
第三部份
用含有磷酸醯胺官能基的配位基
N-(4-methyl-2-pyrimidinyl)-P,P-diphenyl-phosphinic amide (L4) 及
N-(6-methyl-2-pyridinyl)-P,P-diphenyl-phosphinic amide (L5)與過渡金屬鹽類
反應可製備錯合物[Zn(L4)Cl2]∞, 27 ， Co3(L4)4Br6, 28 與
[Ag(L5)(NO3)(CH3CN)]∞, 29。上述錯合物均利用元素分析儀、IR光譜儀與
單晶X-ray繞射儀鑑定之。
配位基L4的分子透過N-H---N與C-H---O氫鍵，以DADA : ADAD與DA :
AD形式的四重及雙重自互補氫鍵形成一維的螺旋鏈狀超分子結構。錯合物
[Zn(L4)Cl2]∞, 27與[Ag(L5)(NO3)(CH3CN)]∞, 29為一維配位高分子鏈狀結
構，其皆為第一個含有磷酸醯胺配位基的配位高分子結構。新型的三核錯
合物Co3(L4)4Br6, 28，其中心金屬藉由配位基L4橋接或螯合形成少見的線型
三核混合Td–Oh–Td構型結構。配位基L4在固態中是以aligned 的構型存
在，在錯合物27與28中橋接模式的L4配位基則是以trans構型存在，在錯合
物28中的螯合配位基則是以cis構型存在；配位基L5在錯合物29中均是以
trans構型存在。
第四部份
三種含有雙四唑配位基4,4'-bis(1-tetrazolyl)diphenyl methane (L6)或
4,4'-bis(1-tetrazolyl)diphenyl ether (L7) 的新型配位高分子錯合物
{[Ag(L6)2](NO3) · 1.6H2O}∞, 30 · 1.6 H2O ， [Cu2Br2(L7)]∞, 31 與
[Cu(L7)2(NO3)2]∞, 32已被合成出來，並利用元素分析儀、IR光譜儀與單晶X-ray繞射儀鑑定之。
配位基L6的分子在固態中，透過C-H---N氫鍵與多種芳香環間的π – π
作用力形成三維的超分子結構。錯合物30、31與32的中心金屬透過配位基
L6或L7的橋接分別是一維扭曲的圈狀鏈、二維的縐摺格子層狀結構以及一
維的圈狀鏈結構。在錯合物30中，共結晶的水分子與硝酸根陰離子透過
O-H---O的氫鍵作用力連結，形成一維氫鍵帶狀超分子結構並穿插於一維的
具有32員環{Ag2N8C22}的陽離子圈狀鏈[14.63 x 13.34 Å2]中，藉此形成三維
的超分子結構。化合物32中，透過配位基L7橋接第二構築單元-一維扭曲的
CuBr鏈，並以此形成二維網狀結構。錯合物32是一維雙股高分子鏈狀結構，
並由M2L2菱形分子格組成32-員環{Cu2N8O2C20}，其菱格大小為10.97 ×
15.87 Å2。在錯合物30 - 32之中，多種形式的配位高分子結構之間透過一系
列的C-H---N氫鍵及多種芳香環間的π – π作用力相互連結形成三維的超分
子結構。

關鍵字

多芽配位基金屬錯合物

並列摘要

This thesis includes four parts discussing the syntheses, structures and
interactions of metal complexes containing mutidentate ligands.
Part I.
The new dipyridyl ligands
N,N'-(methylenedi-p-phenylene)bis-(pyridine-4-carboxamide), L1, and
N,N'-(methylenedi-p-phenylene)bis-(pyridine-3-carboxamide), L2,
incorporating amide spacers have been synthesized. The reactions of CuX2 or
Ag2SO4 with L1 in DMF / H2O produced complexes [CuX2(L1)2]∞ (X = F, 1, X
= Cl, 2 and X = Br, 3), {[Cu(DMF)(L1)2](X)2}∞ (X = NO3
-, 4, X = ClO4
-, 5 and
X = BF4
-, 6), and {[Ag(L1)2](SO4)}∞, 7, while reaction of Cu(NO3)2 ⋅ 3 H2O
with L2 in CH3OH / DMSO solution afforded the complex
{[Cu(L2)(DMSO)2(NO3)](NO3)}∞, 8, respectively. All compounds have been
characterized by EA, IR and TGA spectroscopic methods and the structures of 2,
3, 4, 7 and 8 have been determined by X-ray crystallography, confirming that
complexes 2, 3, 4, 7 and 8 are 1-D coordination polymers.
Complexes 2, 3 and 4 show the 1-D looped polymeric chains with a
nanoporous M2L2 rhombohedral molecular square with an approximately
accessible cavity of 16.95 × 19.13 for 2, 17.03 × 19.06 for 3 and 16.66 × 19.94
Å2 for 4 without any interpenetrations. The 1-D looped chains in complexes 2 –
4 are linking together through CH---X (X = Cl, Br and O) and / or N-H---X
hydrogen bonds to form 3-D supramolecular structures. Complex 7 forms
infinite 1-D zigzag polymeric chain, which is interlinked through a series of
Ag---O interactions to form wavy 1-D ladder like chains. Each 1-D sinusoidal
chain in complex 8 is linked to the other through a series of C-H---O and/or
N-H---O hydrogen bonds and π – π stacking interactions to form 3-D
supramolecular structures.
Part II.
Various new supramolecular complexes with zero-, one- and
two-dimensional structures have been successfully prepared by the reaction of
2,3-diphenylquinoxailne, L3, with Ag(I), Cu(I), Cu(II) and Hg(II) salts in
different solution systems. New complexes were fully characterized by EA and
IR analysis and single-crystal X-ray diffraction.
The complexes [Ag(L3)2](X) (X = ClO4, 9; X = PF6, 10; and X = SbF6, 11)
have mononuclear structures, which are further assembled into 3-D nets via
intermolecular C-H---Ag interactions, Ag---X weak interactions (X = O or F)
and C-H---X hydrogen bonds. The complexes {[Ag(L3)(L’)][X]}∞, (X = BF4, L’
= H2O, 12; X = BF4, L’ = MeCN, 13 and X = ClO4, L’ = MeCN, 14),
[Ag(L3)(CF3SO3) · H2O]∞, 15 · H2O and {[Ag(L3)][SbF6] · 0.5CH2Cl2}∞, 16 ·
0.5CH2Cl2, show the 1-D polymeric infinite chain structures, which are linked
each through anion---π interactions and C-H---X (X = O or F) hydrogen bonds.
The ClO4
- anions in complex 14 interact with the rings in tridentate bonding
mode forming the rare [ClO4-π]n zigzag chain. The dinuclear complex
Ag2(L3)(NO3)2(DMF)2, 17 is further interlinked through interlayer face to face
π – π stacking, Ag---O weak interactions and C-H---O hydrogen bonds, resulting
in a 1-D supramolecular ladder like chains. The complexes
[Ag2(L3)(NO3)2(L’)2]∞ (L’ = H2O, 18 and L’ = MeCN, 19) show the 1-D ladder
like chains, and the [Ag2(L3)]2+ units interlink by H2O molecules and/or NO3
-
anions. The complex [Ag2(L3)(NO3)2]∞, 20 shows the 2-D pleated (6,3) net,
which is regarded as interweaving of -[Ag-L3-Ag-(μ2,η1-NO3)]- chains and
helical –[Ag-(μ2,η1,η1-NO3)-Ag-(μ2,η1-NO3)]- chains. The 2-D pleated grids
[Ag(L3)(p-TsO)]∞, 21, which is regarded as -[Ag-L3]- chains and
-[Ag-(μ2,η1,η1-p-TsO)]- chains. The complex [CuI(L3)]2, 22, has a dimeric
structure with a central Cu2I2 core and each Cu(I) center is coordinated by an N
atom of L3 and two bridging iodide to give three-coordinated coppers. The
monomers CuX2(L3)2, (X = Cl, 23 and X = Br, 24), and HgX2(L3)2, (X = Cl, 25
and X = Br, 26) link each through C-H---X (X = Cl or Br) hydrogen bonds and
π – π stacking interactions to form 2-D supramolecular layers.
It is worth noting that one of the interesting structural features of 9 - 21 is
the presence of obvious C-H---Ag hydrogen-bonding interactions between the
Ag(I) ions and H atoms of quinoxaline group identified by X-ray diffraction on
the basis of the van der Waals radii. In this study, the resulting structural types
of the Ag(I) complexes containing L3 are affected by factors such as counterion,
metal-to-ligand ratio and solvent.
Part III.
The phosphinic amide ligands
N-(4-methyl-2-pyrimidinyl)-P,P-diphenyl-phosphinic amide, L4, and
N-(6-methyl-2-pyridinyl)-P,P-diphenyl-phosphinic amide, L5, were synthesed
and reacted with metal salts to prepare the complexes [Zn(L4)Cl2]∞, 27,
Co3(L4)4Br6, 28 and [Ag(L5)(NO3)(CH3CN)]∞, 29. All compounds have been
characterized by spectroscopic methods and their structures determined by X-ray
crystallography.
The molecules of L4 ligands are interlinked through DADA : ADAD
self-complementary quadruple interactions with two strong N-H---N and two
weak C-H---O hydrogen bonds, and DA : AD double hydrogen bonds to form
the rare 1-D hydrogen-bonded helical chain. The complexes [Zn(L4)Cl2]∞, 27
and [Ag(L5)(NO3)(CH3CN)]∞, 29 show the 1-D polymeric infinite chain
structures, and both of them are the first coordination polymers containing
phosphinic amide ligands. In the new 0-D trinuclear complex Co3(L4)4Br6, 28,
an uncommon linear Co(II) trimers of mixed Td–Oh–Td geometries, the Co(II)
atoms are bridged and cheleated by the L4 ligands.
While the L4 ligand in the solid state adopts aligned conformation and
those bridging ones in complexes 27 and 28 adopt trans conformation and the
cheleating ligands in complex 28 adopt cis conformations, the L5 ligand in
complex 29 adopts the trans conformation.
Part IV.
Three new coordination polymers with large flexible spacer
bis(tetrazol-1-yl) as bridges, {[Ag(L6)2](NO3) · 1.6H2O}∞, 30 · 1.6H2O;
[Cu2Br2(L7)]∞, 31, and [Cu(L7)2(NO3)2]∞, 32, have been synthesized and
characterized, where L6 = 4,4'-bis(1-tetrazolyl)diphenyl methane, and L7 =
4,4'-bis(1-tetrazolyl)diphenyl ether. All compounds have been characterized by
EA and IR spectroscopic methods and their structures have been determined by
X-ray crystallography.
The molecules of L6 ligands are interlinked through the series of C-H---N
hydrogen bonds and various π - π stacking interactions among aromatic rings to
form the 3-D supramolecular structures in solid state. Complexes 30, 31 and 32
show the 1-D flexuous looped chain, 2-D pleated nets, and 1-D looped
polymeric chains with bridging ligands L6 or L7. The co-crystallized water
molecules and nitrate anions in complex 30 form 1-D hydrogen bonded tapes,
which insert into the 1-D looped cationic chains to from the 3-D supramolecular
structures. With L7 as the bridges, the 1-D stair-like CuBr secondary building
units (SBUs) are extended into 2-D network compound 31. Complex 32 shows
the 1-D looped polymeric chains involving M2L2 rhombohedral 32-membered
{Cu2N8O2C20} metallocycles with an approximately accessible cavity of 10.97 ×
15.86 Å2 without any interpenetrations. The polymeric structures in complexes
30 – 32 are linking together through a series of C-H---N hydrogen bonds and
various π - π stacking interactions to form 3-D supramolecular structures.

並列關鍵字

Metal Complexes Containing Multidentate Ligands

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