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首页> 外文期刊>Inorganic Chemistry Frontiers >Hydrophobic tail length in spin crossover active iron(ii) complexes predictably tunes T-1/2 in solution and enables surface immobilisation
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Hydrophobic tail length in spin crossover active iron(ii) complexes predictably tunes T-1/2 in solution and enables surface immobilisation

机译：旋转交叉活性铁（II）复合物在溶液中可预测地调谐T-1/2的疏水性尾部长度，使表面固定能够

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摘要

The literature tetradentate acyclic Schiff base ligand HLH-OH (from the 2 : 1 reaction of pyridine-2-carboxylaldehyde with 1,3-diamino-2-propanol) was alkylated using a range of 1-bromoalkanes varying in length, BrR (R = C10H21, C16H33, C18H37, C20H41 and C22H45) to yield five new ligands, LH-OR. The synthesis, magnetic and Langmuir characteristics of the corresponding family of six neutral mononuclear Fe(ii) complexes, the parent complex [Fe-II(HLH-OH)(NCBH3)(2)] and the five alkylated ligand derivatives [Fe-II(LH-OR)(NCBH3)(2)], is detailed. The solution spin crossover temperature, T-1/2, can be tuned by two methods: (a) increasing the solvent polarity index (P ') from 5 to 7 increases T-1/2 by 172 K, whereas (b) increasing the tail length from C-10 to C-22 decreases T-1/2 by 115 K. In both cases strong linear correlations are observed, so both of these, choice of solvent (R-2 = 0.99, albeit only for three solvents) and of tail length (R-2 = 0.98, for five complexes), are levers for the predictable tuning of the spin state in advance of synthesis. The compounds with longer tails, C-18, C-20 and C-22, showed a small window of thermal hysteresis (<5 K) in D-3-acetonitrile solution. Water solubility hampered the formation of Langmuir films of these complexes. But the use of a 1 : 1 mixture of stearic acid with [Fe-II(LH-OC18)(NCBH3)(2)] facilitated the formation of a stable Langmuir film, a monolayer of which was transferred onto a quartz slide: multi-layering was not possible.
机译：文献四烯烃无环席夫碱配体HLH-OH（来自吡啶-2-羧基二丙基的2：1反应用1,3-二氨基-2-丙醇）使用长度不同的1-溴烷烃烷基化，BRR（r = C10H21，C16H33，C18H37，C20H41和C22H45），得到五种新配体，LH或。相应的六种中性单核Fe（II）配合物的合成，磁性和朗米尔特征，亲本复合物[Fe-II（HLH-OH）（NCBH3）（2）]和五种烷基化配体衍生物[Fe-II （LH-OR）（NCBH3）（2）]详细。溶液自旋交叉温度T-1/2可以通过两种方法进行调节：（a）将溶剂极性指数（p'）增加到7〜7的增加T-1/2×172k，而（b）增加从C-10至C-22的尾长降低T-1/2×115k。在两种情况下，观察到强烈的线性相关性，所以这两种溶剂的选择（R-2 = 0.99，虽然仅适用于三种溶剂）和尾长（R-2 = 0.98，五个配合物）是用于在合成前进的可预测调谐旋转状态的杠杆。具有较长尾，C-18，C-20和C-22的化合物，显示了D-3-乙腈溶液中的热滞后（<5 k）的小窗。水溶解度阻碍了这些配合物的Langmuir薄膜的形成。但是使用1：1与[Fe-II（LH-OC18）（NCBH3）（2）]的硬脂酸混合物促进了形成稳定的Langmuir膜，其单层转移到石英幻灯片上：多重 - 不可能。

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