Electronically labile, or switchable, cobalt coordination polymers exhibit reversible spin crossover (SCO) or valence tautomeric (VT) transitions upon the application of an external stimulus, such as temperature variation. Spin crossover transitions at pseudo-octahedral cobalt(II) centers with an appropriate ligand field involve a heating-induced transition from the low-spin to high-spin electronic configurations. Valence tautomeric transitions are most commonly observed for cobalt-dioxolene systems, which undergo an intramolecular electron transfer and concomitant spin transition at the cobalt center, from low-spin-cobalt(III)-catecholate at low temperature to high-spin-cobalt(II)-semiquinonate upon heating. The VT transition can also be induced by light, while the cobalt(II) SCO transition cannot. Incorporation of these switchable moieties into coordination polymers (CPs) is generally achieved using polytopic nitrogen-donor linking ligands. All but one of the switchable cobalt CPs that have been structurally characterized are 1D chains, most of which exhibit VT transitions rather than SCO. There is a single example of a switchable 2D cobalt CP where VT cobalt-dioxolene moieties are linked by a tetratopic nitrogen-donor bridging ligand. Efforts to confer the VT properties to compounds suitable for applications as materials or in devices have mainly focused on the incorporation of the 1D chain VT CPs into nano- and microparticles, in which the VT transition is generally maintained. Valence tautomeric nanoparticles synthesized from 1D chain CPs have been grafted on to gold surfaces as self-assembled monolayers.

在施加外部刺激（例如温度变化）时，电子不稳定或可切换的钴配位聚合物表现出可逆的自旋交联（SCO）或价互变异构（VT）跃迁。在伪八面体钴（II）中心具有适当配体场的自旋交叉跃迁涉及从低自旋电子构型到高自旋电子构型的加热诱导跃迁。价-互变异构过渡最常见于钴-二氧杂环戊烯体系，该体系在钴中心经历分子内电子转移和伴随的自旋跃迁，从低温的低自旋钴（III）-儿茶酚盐到高自旋的钴（II） ）-加热时的半奎宁酸酯。VT跃迁也可以由光引起，而钴（II）SCO跃迁则不能。这些可转换部分并入配位聚合物（CP）中通常是使用多氮原子供体连接配体实现的。除了结构上已被表征的可切换钴CP以外，其余所有都是1D链，其中大多数显示VT过渡而不是SCO。有一个可转换的2D钴CP的例子，其中VT钴-二氧杂环戊烯基团通过一个四位氮供体桥联配体相连。赋予适合于作为材料或在设备中应用的化合物VT特性的努力主要集中在将一维链VT CP掺入通常保持VT过渡的纳米和微粒中。由一维链CP合成的化合价互变异构纳米粒子已作为自组装单层嫁接到金表面。