期刊
INORGANIC CHEMISTRY
卷 59, 期 8, 页码 5433-5446出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c00008
关键词
-
资金
- College of Natural Sciences and Mathematics (CNSM)
- University Research Council (URC) from the University of Central Arkansas
- Arkansas Science & Technology Authority (ASTA) from the State of Arkansas
- NSF [CCLI 0125711, 1856438]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1856438] Funding Source: National Science Foundation
A group of copper complexes supported by polydentate pyridylamide ligands H(2)bpda and H(2)ppda were synthesized and characterized. The two Cu(II) dimers [Cu-2(II)(Hbpda)(2)(ClO4)(2)] (1) and [Cu-2(II)(ppda)(2)(DMF)(2)] (2) were constructed by using neutral ligands to react with Cu(II) salts. Although the dimers showed similar structural features, the second-sphere interactions affect the structures differently. With the application of Et3NT, the tetranuclear cluster (HNEt3)[Cu-4(II)(bpda)(2)(mu(3)-OH)(2)(ClO4)(DMF)(3)](ClO4)(2) (3) and hexanuclear cluster (HNEt3)(2)[Cu-6(II)(ppda)(6)(H2O)(2)(CH3OH)(2)](ClO4)(2) (4) were prepared under similar reaction conditions. The symmetrical and unsymmetrical arrangement of the ligand donors in ligands H(2)bpda and H(2)ppda led to the dramatic conformation difference of the two Cu(II) complexes. As part of our effort to explore mixed-valence copper chemistry, the triple-decker pentanuclear cluster [(Cu3Cu2I)-Cu-II (bpda)(3)(mu(3)-O)] (5) was prepared. XPS examination demonstrated the localized mixed-valence properties of complex 5. Magnetic studies of the clusters with EPR evidence showed either weak ferromagnetic or antiferromagnetic interactions among copper centers. Due to the trigonal-planar conformation of the trinuclear Cu(II) motif with the mu(3)-O center, complex 5 exhibits geometric spin frustration and engages in antisymmetric exchange interactions. DFT calculations were also performed to better interpret spectroscopic evidence and understand the electronic structures, especially the mixed-valence nature of complex 5.
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