{[Hg(SCN)3]2(μ-L)}2–: An Efficient Secondary Building Unit for the Synthesis of 2D Iron(II) Spin-Crossover Coordination Polymers,Inorganic Chemistry

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{[Hg(SCN)3]2(μ-L)}2–: An Efficient Secondary Building Unit for the Synthesis of 2D Iron(II) Spin-Crossover Coordination Polymers
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02906
Daopeng Zhang _{1,

2} , Francisco Javier Valverde-Muñoz ₁ , Carlos Bartual-Murgui ₁ , Lucía Piñeiro-López ₁ , M. Carmen Muñoz ₃ , José Antonio Real ₁

Affiliation

We report an unprecedented series of two-dimensional (2D) spin-crossover (SCO) heterobimetallic coordination polymers generically formulated as {Fe^II[(Hg^II(SCN)₃)₂](L)_x}·Solv, where x = 2 for L = tvp (trans-(4,4′-vinylenedipyridine)) (1tvp), bpmh ((1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine) (1bpmh·nCH₃OH; n = 0, 1), bpeh ((1E,2E)-1,2-bis(1-(pyridin-4-yl)ethylidene)hydrazine) (1bpeh·nH₂O; n = 0, 1) and x = 2.33 for L = bpbz (1,4-bis(pyridin-4-yl)benzene) (1bpbz·nH₂O; n = 0, 2/3). The results confirm that self-assembly of Fe^II, [Hg^II(SCN)₄]^2–, and ditopic rodlike bridging ligands L containing 4-pyridyl moieties favors the formation of linear [Fe(μ-L)]_n²ⁿ⁺ chains and in situ generated binuclear units {[Hg^II(SCN)₃]₂(μ-L)}^2–. The latter act as bridges between adjacent chains generating robust 2D layers. The [Fe^IIN₆] centers are equatorially surrounded by four NCS^– groups and two axial N atoms of the organic ligand L. The compound 1tvp and the unsolvated form of 1bpmh undergo complete SCO centered at T_1/2 = 177 and 226 K, characterized by the enthalpy and entropy variations ΔH = 12.3 and 10.5 kJ mol^–1 and ΔS = 69.4 and 48 J K^–1 mol^–1, respectively. The almost complete SCO of the unsolvated form of 1bpeh occurs at ca. T_1/2 = 119 K and exhibits a complete LIESST effect. Regardless of the degree of solvation, a half-spin conversion at T_1/2 < 100 K occurs for 1bpbz·nH₂O, which becomes almost complete at p = 0.65 GPa. The labile solvent molecules present in 1bpmh·CH₃OH and 1bpeh·H₂O have a dramatic influence on the corresponding SCO behavior.

中文翻译：

{[Hg（SCN）₃ ] ₂（μ-L）} ^2–：用于合成二维铁（II）自旋交叉配位聚合物的高效二级结构单元

我们报告了前所未有的一系列二维（2D）自旋交联（SCO）异双金属配位聚合物，通常被定义为{Fe ^II [（Hg ^II（SCN）₃）₂ ]（L）_x }·Solv，其中x = 2对于L = tvp（反式-（4,4'-乙烯基二吡啶））（1tvp），bpmh（（1 E，2 E）-1,2-双（吡啶-4-基亚甲基）肼）（1bpmh· n CH ₃ OH ; n = 0，1），bpeh（（1 E，2 E）-1,2-双（1-（吡啶-4-基）亚乙基）肼）（1bpeh· n H₂ O ; Ñ = 0，1）和X为L = 2.33 = bpbz（1,4-二（吡啶-4-基）苯）（ 1bpbz· Ñ ħ ₂ ö ; Ñ = 0，2/3）。结果证实，Fe^II，[Hg^II（SCN）₄ ]^2–和含有4-吡啶基部分的对位棒状桥联配体L的自组装有利于线性[Fe（μ-L）]_n^{2 n +的形成。}链和原位生成的双核单位{[Hg^II（SCN）₃ ]₂（μ-L）}^2–。后者充当相邻链之间的桥梁，从而生成坚固的2D层。所述的[Fe ^II Ñ ₆ ]中心由四个NCS个平展包围^-基团和有机配体L的化合物的两个轴向N原子1tvp和未溶剂化的形式1bpmh进行完全SCO居中在Ť _1/2 = 177和226ķ ，其特征在于焓变和熵变ΔH = 12.3和10.5 kJ mol ^–1，ΔS = 69.4和48 JK ^–1 mol ^–1。未溶剂化形式的1bpeh的几乎完整的SCO发生在大约。Ť_1/2 = 119 K，并表现出完全的LIESST效果。无论溶剂化程度如何，对于1bpbz· n H ₂ O，在T _1/2 <100 K时都会发生半自旋转化，在p = 0.65 GPa时几乎完成。1bpmh·CH ₃ OH和1bpeh·H ₂ O中存在的不稳定溶剂分子对相应的SCO行为具有显着影响。

更新日期：2018-01-16

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