新型CuII/4,4'-联吡啶方格聚合物的表征与结构解析

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本文是一篇深入探讨的学术论文，主要研究了新型的铜(II)离子/4,4'-联吡啶配合物聚合物，其中包含特殊的方形网格结构。作者们是来自阿根廷La Plata地区的 Patricia A. M. Williams、Evelina G. Ferrer 和 Enrique J. Baran，他们分别在CEQUINOR（CONICET/UNLP）和大学科学学院工作。此外，论文还包含了Oscar E. Piro 的贡献，他在物理部门和Instituto IFLP也参与了研究。研究的核心焦点是化合物[Cu(4,4'-bipy)2(H2O)2]-(sac)2·DMF，其中4,4'-bipy指的是4,4'-联吡啶，sac是 saccharin（环己二胺）的阴离子，而DMF则是 dimethylformamide（二甲基亚砜）。通过单晶X射线衍射技术，研究人员成功解析了这种新型聚合物的晶体结构。晶体具有orthorhombic（正交）空间群Pcnb，其晶格参数为a = 14.4994(2) Å，b = 15.8128(3) Å，c = 16.6850(2) Å，空间群对称性为Z = 4，这表明它形成了一种具有高度有序结构的方形网格聚合物。论文的摘要部分提到了研究的目的，即尝试制备出新的方形网格聚合物，并且这项工作展示了在化学合成与晶体结构分析之间的紧密合作。通过这种新型CuII/4,4'-bipyridine配合物聚合物的研究，科学家们不仅加深了我们对这类材料的理解，也为未来可能的应用提供了理论基础，如材料科学中的催化剂、电导体或光电子学材料等领域。这篇论文对于理解金属有机框架（MOFs）中的结构设计和功能调控有着重要意义，因为方形网格结构通常赋予MOFs独特的孔隙性和高比表面积，这对于气体存储、分离以及催化作用至关重要。因此，它对于材料化学家、结晶学家和材料工程师来说是一篇不可忽视的重要文献。

Characterization of a Novel Cu

/4,4’-Bipyridine Coordination Polymer

Containing Square Grids

Patricia A. M. Williams, Evelina G. Ferrer, and Enrique J. Baran*

La Plata/Argentina, CEQUINOR (CONICET/UNLP), Facultad de Ciencias Exactas, Universidad Nacional de la Plata

Oscar E. Piro

La Plata/Argentina, Departamento de Fi

sica and Instituto IFLP, Facultad de Ciencias Exactas, Universidad Nacional de La Plata

Eduardo E. Castellano

o Carlos (SP)/Brazil, Instituto de Fisica de Sa

o Carlos, Universidade de Sa

o Paulo

Received May 7

, 2002.

Abstract. In an attempt to obtain new square grid polymers we

could prepare the copper(II) complex [Cu(4,4’-bipy)

(sac)

· DMF (4,4’-bipy ⫽ 4,4’-bipyridine; sac ⫽ anion of sac-

charin; DMF ⫽ dimethylformamide). Its structure was determined

by single crystal X-ray diffraction methods. It crystallizes in the

orthorhombic space group Pcnb (a ⫽ 14.4994(2), b ⫽ 15.8128(3),

c ⫽ 16.6850(2) A

,Z⫽ 4) and is a square grid polymer with the

Charakterisierung eines neuartigen, viereckige Gitter enthaltenden Cu

/4,4’-Bipyridin

Koordinationspolymer

Inhaltsübersicht. Bei Versuchen neue viereckige Gitter-Polymere zu

erhalten, gelang es den Kupfer(II)-Komplex [Cu(4,4’-bipy)

(sac)

· DMF (4,4’-bipy ⫽ 4,4’-Bipyridin; sac ⫽ Anion des Saccha-

rins; DMF ⫽ Dimethylformamid) darzustellen. Seine Struktur

wurde röntgenographisch an Einkristallen bestimmt. Er kristalli-

siert in der orthorhombischen Raumgruppe Pcnb ( a ⫽ 14.4994(2),

1 Introduction

Crystal engineering offers potential applications for the

synthesis and development of new crystalline materials, in

particular for those with functional properties as micropo-

rous solids for molecular absorption, ion exchange and het-

erogeneous catalysis [1⫺12].For example, metal-organic

networks can be designed through coordination chemistry

methodologies and the obtained materials may mimic the

properties of zeolites and clays. In this context, several co-

ordination polymers containing 4,4’-bipyridine (4,4’-bipy)

and other bridging ligands with transition metal cations,

that form molecular binding blocks, have been synthesised

[2⫺12]. The 4,4’-bipy has been selected because of its rod

*Prof.Dr.E.J.Baran

CEQUINOR, Facultad de Ciencias Exactas, UNLP

C.Correo 962, 1900-La Plata/Argentina

FAX: (54) 221-425 9485

E-mail: baran@quimica.unlp.edu.ar

2044  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/2044⫺2048 $ 20.00⫹.50/0 Z. Anorg. Allg. Chem. 2002, 628, 2044⫺2048

saccharinate anions sandwiched between the complex layers and

the DMF molecules filling the square holes. UV-vis, diffuse reflec-

tance and IR spectra, room temperature magnetic susceptibility

and the thermal behaviour were also investigated.

Keywords: Copper; 4,4’-Bipyridine; Crystal structure; Spectroscopic

properties; Thermal behaviour

b ⫽ 15.8128(3), c ⫽ 16.6850(2) A

,Z⫽ 4) und bildet ein viereckiges

Polymer-Gitter mit den Saccharinat-Anionen zwischen den Kom-

plex-Schichten und mit den DMF-Molekülen in viereckigen Lüc-

ken. UV-vis-, Reflexions- und IR-Spektren, sowie die magnetische

Suszeptibilität (bei Raumtemperatur) und das thermische Verhal-

ten, wurden auch untersucht.

like rigidity and length. Some of these networks are square

grid polymers which have guest molecules included in their

pores. Other ligands such as 1,4-bis(4-pyridyl)benzene and

1,4-bis(4-pyridyl)anthracene [13] have been used in order to

obtain different square grid dimensions.

As a part of our current studies on mixed metal sacchar-

inate (saccharin ⫽ o-sulphobenzimide ⫽ C

S) com-

plexes [14⫺18] we have now attempted to prepare this type

of polymeric complexes, containing this anion. In this paper

we present the preparation and characterisation of the coor-

dination square grid polymer [Cu(4,4’-bipy)

](sac)

· DMF.

2 Results and Discussion

2.1 Structural analysis

Crystal parameters and details of the used refinement pro-

cedures are given in Table 1, whereas Fig. 1 shows an

ORTEP [19] drawing of the molecule including the used

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新型CuII/4,4'-联吡啶方格聚合物的表征与结构解析

Characterization of a Novel CuII/4, 4'-Bipyridine Coordination Polymer Containing Square Grids

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