期刊
JOURNAL OF MATERIALS CHEMISTRY
卷 22, 期 20, 页码 10249-10254出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2jm15778k
关键词
-
资金
- Deutsche Forschungsgemeinschaft [SPP-1362, SFB-558]
We have used density functional theory calculations to study non-periodic model systems for the ubiquitous layer-pillar metal organic frameworks built from paddle-wheel building blocks. Experimentally, these porous materials show nearly identical structures for both copper and zinc forming the paddle-wheel, but differ depending on the type of the metal center in their properties. Our theoretical results clearly reveal orbital directing effects for the d(9) Cu(II) center, enforcing a square planar conformation, to be the main reason for the difference in contrast to the flexible d(10) Zn(II) system. Surprisingly, this difference is directly visible in the structure of the bare vertex model without axial ligands, whereas in the case of pyridine coordination both copper and zinc complexes are structurally nearly indistinguishable. However, in the vibrational normal modes the higher degree of flexibility for the zinc-based systems is still noticeable, explaining the higher flexibility of the corresponding periodic MOFs.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据