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 Ln^III-bpdo-W^V(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.

中文翻译：

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一系列镧系元素（III）-bpdo-十氰基钨酸盐（V）化合物（bpdo = 4,4'-联吡啶-N，N'-二氧化物），涉及通过二维从离子对到三维柱状层的结构转化层

辛酸金属钛酸盐[W（CN）₈ ] ^3–，镧系元素离子和4,4'-联吡啶基-N，N'-二氧化物（bpdo）的缓慢扩散反应生成了一系列等构三维柱状网络，具有通式[Ln（bpdo）_1.5（H ₂ O）W（CN）₈ ]·0.5CH ₃ OH·6H ₂O（Ln = Dy–Yb，Gd），其中Ln（III）原子在基于氰金属酸盐的镧系元素中采用不寻常的七配位几何形状。这种同时使用氰化物和bpdo桥的构建方法为设计和构建高维5d-4f配位网络提供了潜在的可能性。有趣的是，Ln ^III -bpdo-W ^V（CN）₈随着扩散反应时间的延长，该系统经历了独特的两步相变，并且结构从最初的离子对通过二维层到最终的三维柱状层网络发生了变化。对所有化合物的磁性研究表明，自旋中心之间的弱耦合相互作用具有典型且占优势的单离子磁性行为。