Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, 1060 Vienna, Austria.
Dalton Trans. 2020 Dec 15;49(47):17183-17193. doi: 10.1039/d0dt03315d.
To increase the supramolecular cooperativity in Fe(ii) spin crossover materials based on N1-substituted tetrazoles, a series of ω-(1H-tetrazol-1-yl) carboxylic acids with chain-lengths of C2-C4 were synthesized. Structural characterization confirmed the formation of a strong hydrogen-bond network, responsible for enhanced cooperativity in the materials and thus largely complete spin-state transitions for the ligands with chain lenghts of C2 and C4. To complement the structural and magnetic investigation, electronic spectroscopy was used to investigate the spin-state transition. An initial attempt to utilize the bifunctional coordination ability of the ω-(1H-tetrazol-1-yl) carboxylic acids for preparation of mixed-metallic 3d-4f coordination polymers resulted in a novel one-dimensional gadolinium-oxo chain system with the ω-(1H-tetrazol-1-yl) carboxylic acid acting as μ2-η2:η1 chelating-bridging ligand.
为了提高基于 N1-取代四唑的 Fe(ii)自旋交叉配合物的超分子协同性，我们合成了一系列链长为 C2-C4 的 ω-(1H-四唑-1-基)羧酸。结构表征证实了强氢键网络的形成，这是材料中协同性增强的原因，从而使配体的自旋态转变几乎完全发生在链长为 C2 和 C4 的化合物中。为了补充结构和磁性研究，我们还使用电子光谱来研究自旋态转变。我们最初尝试利用 ω-(1H-四唑-1-基)羧酸的双官能团配位能力来制备混合金属 3d-4f 配位聚合物，结果得到了一种新型的一维钆氧链体系，其中 ω-(1H-四唑-1-基)羧酸作为 μ2-η2:η1 螯合桥联配体。
