Silver Ion-Mediated Heterometallic Three-Fold Interpenetrating Uranyl-Organic Framework.
A unique case of a uranyl-silver heterometallic 3-fold interpenetrating network (U-Ag-2,6-DCPCA) from a multifunctionalized organic ligand, 2,6-dichloroisonicotinic acid, in the presence of uranyl and silver ions is reported. It is the first report of a heterometallic uranyl-organic interpenetrating network or framework. Notably, a (4,4)-connected uranyl building unit in U-Ag-2,6-DCPCA, which is available through combined influences of structural halogenation and silver ion additive on uranyl coordination, plays a vital role in the formation of a 3-fold interpenetrating network. Halogen substitution effectively changes structural features and coordination behaviors of isonicotinate ligand and contributes to the control of uranyl coordination. Meanwhile, it exerts influence on the stabilization of 3-fold interpenetrating networks by halogen-halogen interactions. Theoretical calculation suggests that the silver ion should mainly serve as an inductive factor of uranyl species through strong Ag-N binding affinity, directly leading to the formation of a (4,4)-connected uranyl building unit and finally a heterometallic 3-fold interpenetrating network. Related experimental results, especially an interesting postsynthetic metalation, afford further evidence of this induction effect.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
Lei
L
Mei
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
Qun-yan
QY
Wu
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
Shu-wen
SW
An
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
Zeng-qiang
ZQ
Gao
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.|School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University , Suzhou 215123, China.
Zhi-fang
ZF
Chai
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
Wei-qun
WQ
Shi