Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units

The principal structure possibilities for packing infinite rod-shaped building blocks are described.
Some basic nets derived from linking simple rods (helices and ladders) are then enumerated. We
demonstrate the usefulness of the concept of rod secondary building units in the design and synthesis of
metal−organic frameworks (MOFs). Accordingly, we present the preparation, characterization, and crystal
structures of 14 new MOFs (named MOF-69A−C and MOF-70−80) of 12 different structure types, belonging
to rod packing motifs, and show how their structures are related to basic nets. The MOFs reported herein
are of polytopic carboxylates and contain one of Zn, Pb, Co, Cd, Mn, or Tb. The inclusion properties of the
most open members are presented as evidence that MOF structures with rod building blocks can indeed
be designed to have permanent porosity and rigid architectures.

本研究阐述了无限长棒状结构基元的主要堆积结构可能性。随后枚举了由简单棒体（螺旋链与梯状链）连接得到的若干基础拓扑网。我们论证了棒状次级结构单元（rod secondary building units）概念在金属有机框架（metal−organic frameworks, MOFs）设计与合成中的应用价值。据此，我们报道了14种新型MOFs（命名为MOF-69A-C与MOF-70-80）的制备、表征与晶体结构，这些材料分属12种不同的结构类型，均遵循棒状堆积基元模式，并阐明了其结构与基础拓扑网的关联方式。本文报道的MOFs均采用多齿羧酸盐配体，所含金属离子为Zn、Pb、Co、Cd、Mn或Tb中的一种。我们通过表征其中孔道最开放的几款材料的客体包合性能，证明了采用棒状结构基元构建的MOF确实可被设计为具有永久孔隙率与刚性骨架的结构。