甘氨酸联接的双金属配合物：Mn(phen)2(C5H6O4)4/2与Zn(phen)(H2O)(C5H6O4)2/2·H2O的结...
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本文报道了两例由Glutaric Acid (H2L)作为桥连配体形成的格拉塔托桥连配位聚合物：1）[Mn(phen)]2L4/2（编号1）和2）[Zn(phen)(H2O)]L2/2·H2O（编号2）。这两者分别在单晶X射线衍射数据的支持下得到了结构表征。1号化合物1采用空间群P2/c（No.13），晶体参数包括a=10.340 Å、b=10.525 Å、c=13.891 Å以及β=98.31°，空间群指标Z=2。其结构特征是一维带状的[Mn(phen)]2(C5H6O4)4/2链，锰原子通过两个Glutaric酸根离子形成8-和16元环，每个Mn原子被两个N原子六面体配位。
而2号化合物2的晶体结构属于P21/n（No.14），具体参数为a=6.738 Å、b=25.636 Å、c=10.374 Å，β=106.13°，空间群指标Z=4。这个化合物中的Zn(phen)(H2O)单元通过Glutaric酸配体相连，形成了更为复杂的三维构型。Zn原子被一个苯环上的N原子和一个水分子协同配位。
这两项研究不仅揭示了格拉塔酸在金属有机框架中的重要作用，还提供了关于多孔材料设计的新思路，展示了不同金属与配体组合可以构建出各异的拓扑结构。这对于理解金属-有机骨架的结构-性能关系，以及开发新型功能材料如催化剂、传感器或吸附剂具有重要意义。此外，单晶X射线衍射技术的应用，进一步验证了理论计算在预测和解释复杂无机结构方面的有效性。整个研究过程体现了合成化学与结构化学的紧密结合，是现代无机化学领域的一个重要贡献。
Two Glutarato Bridged Coordination Polymers:
1
`
{[Mn(phen)]
2
L
4/2
} and
1
`
{[Zn(phen)(H
2
O)]L
2/2
}·H
2
O with H
2
L 5 Glutaric Acid
Yue-Qing Zheng
a,*
, Wen-Han Liu
b
, and Jian-Li Lin
a
a
Ningbo/P. R. China, Municipal Key Laboratory of Inorganic Materials Chemistry, Institute for Solid State Chemistry, Ningbo
University
b
Hangzhou/P. R. China, Department of Chemical Engineering, Zhejiang University of Technology
Received August 29th, 2001.
Abstract. Two new glutarato bridged coordination polymers
1
`
{[Mn(phen)]
2
(C
5
H
6
O
4
)
4/2
}(1) and
1
`
{[Zn(phen)(H
2
O)](C
5
H
6
O
4
)
2/
2
}•· H
2
O(2) were structurally characterized on the basis of single
crystal X-ray diffraction data. Crystal data: (1) P2/c (no. 13), a 5
10.340(2) A
˚
, b 5 10.525(2) A
˚
, c 5 13.891(2) A
˚
, β 5 98.31(1)°, U 5
1495.9(5) A
˚
3
, Z 5 2; (2) P2
1
/n (no. 14), a 5 6.738(1) A
˚
, b 5
25.636(3) A
˚
, c 5 10.374(1) A
˚
, β 5 106.13(1)°, U 5 1721.4(4) A
˚
3
,
Z 5 4.
Complex 1 consists of 1D ribbon-like
1
`
{[Mn(phen)]
2
(C
5
H
6
O
4
)
4/2
}
chains, in which the [Mn(phen)] units were interlinked by glutarato
ligands to generate 8- and 16-membered rings. The Mn atoms are
octahedrally coordinated by two N atoms of one phen ligand and
four O atoms of three glutarato ligands with d(Mn-N) 5 2.270,
2.276 A
˚
, d(Mn-O) 5 2.11422.283 A
˚
. Through the interchain π-π
stacking interactions, the 1D chains are assembled into 2D puck-
Zwei Glutarato-verbrückte Koordinationspolymere:
1
`
{[Mn(phen)]
2
L
4/2
} und
1
`
{[Zn(phen)(H
2
O)]L
2/2
}·H
2
O mit H
2
L 5 Glutarsäure
Inhaltsübersicht. Zwei neue Glutarato-verbrückte Koordination-
spolymere
1
`
{[Mn(phen)]
2
(C
5
H
6
O
4
)
4/2
} (1) und
1
`
{[Zn(phen)-
(H
2
O)](C
5
H
6
O
4
)
2/2
}•H
2
O(2) wurden strukturell charakterisiert mit
röntgnographischen Methoden. Einkristalldaten: (1) P2/c (Nr. 13),
a 5 10,340(2) A
˚
, b 5 10,525(2) A
˚
, c 5 13,891(2) A
˚
, β 5 98,31(1)°,
U 5 1495,9(5) A
˚
3
, Z 5 2; (2) P2
1
/n (Nr. 14), a 5 6,738(1) A
˚
, b 5
25,636(3) A
˚
, c 5 10,374(1) A
˚
, β 5 106,13(1)°, U 5 1721,4(4) A
˚
3
,
Z 5 4. Der Komplexe 1 besteht aus bandfömigen
1
`
{[Mn(phen)]
2
(C
5
H
6
O
4
)
4/2
}-Ketten, in denen die [Mn(phen)]-Bau-
einheiten über die Glutarat-Liganden unter Bildung von den 8-
bzw. 16-gliederigen Ringen miteinander verbunden sind. Die Mn-
Atome sind jeweils von zwei N-Atomen eines Phen-Liganden und
vier O-Atomen dreier Glutarato-Liganden oktaederisch koordiniert
mit d(Mn-N) 5 2,270, 2,276 A
˚
, d(Mn-O) 5 2,11422,283 A
˚
. Durch
Introduction
In recent years, both aromatic diimine complexes of Mn
and Zn have been widely investigated [126]. The main rea-
* Prof. Dr. Yue-Qing Zheng
Institute for Solid State Chemistry
Ningbo University, Ningbo
315211 P. R. China
Telefax: Int. 1574/87600747
e-mail: zhengcm@nbu.edu.cn
824
WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 004422313/02/628/8242828 $ 20.001.50/0 Z. Anorg. Allg. Chem. 2002, 628,8242828
ered layers, which are further held together by interlayer π-π stack-
ing interactions into a 3D network. Complex 2 isbuiltupby1D
1
`
{[Zn(phen)(H
2
O)](C
5
H
6
O
4
)
2/2
} linear chains and hydrogen
bonded H
2
O molecules. The Zn atoms are coordinated by two N
atoms of one phen ligand and three O atoms of one H
2
O molecule
and two glutarato ligands to form slightly elongated trigonal bi-
pyramids with the water O atom and one phen N atom at the apical
positions (d(Zn-N) 5 2.101, 2.168 A
˚
, d(Zn-O) 5 1.99122.170 A
˚
).
The 1D linear chains result from [Zn(phen)(H
2
O)] units bridged
by bis-monodentate glutarato ligands. The resulting 1D chains are
assembled by π-π stacking interactions into 2D layers, between
which the hydrogen bonded H
2
O molecules are situated.
Keywords: Manganese; Zinc; Glutarato complexes; Phen com-
plexes; π-π Stacking interactions
die π-π-Wechselwirkungen werden die 1D-Ketten zu den gewellten
2D-Schichten zusammengehalten, die wiederum zu einem 3D-Net-
zwerk verbunden sind. Der Komplexe 2 ist aus
1
`
{[Zn(phen)-
(H
2
O)](C
5
H
6
O
4
)
2/2
}-Ketten und den über H-Brücken gebundenen
H
2
O-Molekülen aufgebaut. Die Zn-Atome sind jeweils von zwei
N-Atomen eines Phen-Liganden und drei O-Atomen aus H
2
O-Mo-
lekülen und zwei Glutarato-Liganden trigonal-bipyramidal koordi-
niert, mit dem Wasser-O-Atom und einem Phen-N-Atom an den
apikalen Stellen (d(Zn-N) 5 2,101, 2,168 A
˚
, d(Zn-O) 5
1,99122,170 A
˚
). Die 1D-Ketten resultieren aus den
[Zn(phen)(H
2
O)]-Baueinheiten, die über bis-einzähnigen Gluta-
rato-Liganden verknüpft sind; sie werden durch π-π-Wechselwir-
kungen zu 2D-Schichten verbunden, zwischen denen die über H-
Brücken gebundenen H
2
O-Moleküle lokalisiert sind.
son may be that the aromatic diimine such as bipy and
phen can be used as ligands to generate models of metal-
loenzyme active sites [7210] and sites of molecular recogni-
tion [11, 12], and that both, Mn and Zn, are essential trace
elements to all forms of life and a large number of diseases
and congenital disorders have been traced to their defi-
ciency. Futhermore, manganese has been recognized to be
an essential component of the photosynthetic mechanism
in green plants and it appears to function as a redox cata-
lyst in the part of the mechanism, photosystem-II, in which
water is oxidized to dioxygen [13]. On the other hand,
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