Construct Polyoxometalate Frameworks through Covalent Bonds.
An emerging strategy for exploring the application of polyoxometalates (POMs) is to assemble POM clusters into open-framework materials, especially inorganic-organic hybrid three-dimensional (3D) open-framework materials, via the introduction of different organic linkers between the POM clusters. This strategy has yielded a few 3D crystalline POMs of which a typical class is the group of polyoxometalate metal-organic frameworks (POMMOFs). However, for reported POMMOFs, only coordination bonds are involved between the linkers and POM clusters, and it has not yet produced any covalently bonded polyoxometalate frameworks. Here, the concept of "covalently bonded POMs (CPOMs)" is developed. By using vanadoborates as an example, we showed that the 3D CPOMs can be obtained by a condensation reaction through the oxolation mechanism of polymer chemistry. In particular, suitable single crystals were harvested and characterized by single-crystal X-ray diffraction. This work forges a link among polymer science, POM chemistry, and open-framework materials by demonstrating that it is possible to use covalent bonds according to polymer chemistry principles to construct crystalline 3D open-framework POM materials.
Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University , SE-106 91 Stockholm, Sweden.|Faculty of Material Science and Chemistry, China University of Geosciences , 430074 Wuhan, China.
Hong
H
Chen
Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University , SE-106 91 Stockholm, Sweden.|Faculty of Pharmaceutical and Environment Technology, Changzhou Institute of Engineering Technology , 213164 Changzhou, China.
Huishuang
H
Zhao
College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
Zheng-Bao
ZB
Yu
Organic Chemistry, Center of Molecular Devices, School of Chemical Science and Engineering, KTH Royal Institute of Technology , 100 44 Stockholm, Sweden.
Lei
L
Wang
Organic Chemistry, Center of Molecular Devices, School of Chemical Science and Engineering, KTH Royal Institute of Technology , 100 44 Stockholm, Sweden.
Licheng
L
Sun
Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University , SE-106 91 Stockholm, Sweden.|College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
Junliang
J
Sun