A Series of Lanthanide(III)-bpdo-Octacyanotungstate(V) Compounds (bpdo = 4,4′-Bipyridine‑N,N′‑dioxide) Involving the Structural Transformation from Ion Pair to Three-Dimensional Pillared Layer via a Two-Dimensional Layer

• Published in: Crystal growth & design 2017-12, Vol.17 (12), p.6523-6530
• Main Authors: Zhou, Hu, Chen, Qi, Yuan, Ai-Hua, Zhou, Hong-Bo, Shen, Xiao-Ping, Chen, Lei, Song, You
• Format: Article
• Language: English
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.7b01196

The slow diffusion reaction of octacyanometalate [W­(CN)8]3–, lanthanide ions, and 4,4′-bipyridyl-N,N′-dioxide (bpdo) has generated a series of isostructural three-dimensional pillared-layer networks with general formula [Ln­(bpdo)1.5(H2O)­W­(CN)8]­·0.5CH3OH­·6H2O (Ln = Dy–Yb, Gd), in which Ln­(III) atoms adopted an unusual seven-coordinated geometry in the cyanometalate-based lanthanide system. This building approach on the basis of the simultaneous employment of cyanide and bpdo bridges offers potential possibilities for designing and constructing 5d-4f coordination networks with high dimensionalities. Interestingly, the LnIII-bpdo-WV(CN)8 system has undergone an unique two-step phase transition upon prolonging the diffusion reaction time, together with the structural changing from initial ion pair through two-dimensional layer to final three-dimensional pillared-layer network. Magnetic studies of all compounds revealed typical and dominant single-ion magnetic behaviors over the weak coupling interactions between spin centers.