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Simultaneous Introduction of Two Nitroxides in the Reaction: A New Approach to the Synthesis of Heterospin Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-13 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02308
Victor Ovcharenko 1 , Olga Kuznetsova 1 , Elena Fursova 1 , Gleb Letyagin 1 , Galina Romanenko 1 , Artem Bogomyakov 1 , Ekaterina Zueva 2
Affiliation  

A new approach to the synthesis of multispin compounds has been developed, namely, the simultaneous introduction of two different stable nitroxides (nitronyl nitroxide and imino nitroxide) in a reaction with a metal ion. An important characteristic of the new method is that nitronyl nitroxide and imino nitroxide introduced in the reaction with the metal are the products of different series; i.e., the nitronyl nitroxide molecule differs from the imino nitroxide molecule not only in one additional oxygen molecule per molecule but also in another substituent in the side chain of the organic paramagnet. This possibility was demonstrated on the synthesis of multispin compounds [Ni2(A1)(L2)2(Piv)(MeOH)], [Ni2(L1)(A2)2(Piv)(H2O)], [Co2(A1)(L2)2(Piv)(MeOH)], and [Co3(L1)2(A2)2(Piv)2], in which Ln and An differ in the substituent in the phenyl ring. The number of multispin compounds that can be synthesized by the proposed method is almost unlimited. The heterospin complexes of transition metals with coordinated nitronyl nitroxide and imino nitroxide in one molecule contain energy-different exchange interaction channels that differ in both magnitude and sign, as confirmed by the quantum-chemical analysis of exchange channels in [Ni(B1)(B2)2](NO3)2. The series of mixed-radical complexes may include compounds with nontrivial magnetic properties such as [Co2(A1)(L2)2(Piv)(MeOH)], which experiences bulk magnetic ordering below 3.5 K.

中文翻译:

在反应中同时引入两种氮氧化物:杂多旋复合物合成的新方法

已经开发了一种合成多旋化合物的新方法,即在与金属离子的反应中同时引入两种不同的稳定氮氧化物(亚硝酰基氮氧化物和亚氨基亚硝酸盐)。该新方法的一个重要特点是与金属反应引入的亚硝酰基氮氧化物和亚氨基氮氧化物是不同系列的产物。即,亚硝酰基氮氧化物分子与亚氨基氮氧化物分子的不同之处不仅在于每个分子一个额外的氧分子,而且还在于有机顺磁体侧链中的另一个取代基。多旋化合物[Ni 2(A 1)(L 22(Piv)(MeOH)],[Ni2(L 1)(A 22(Piv)(H 2 O)],[Co 2(A 1)(L 22(Piv)(MeOH)]和[Co 3(L 12( A 22(Piv)2 ],其中L n和A n苯环上的取代基不同。可以通过提出的方法合成的多旋化合物的数量几乎是无限的。一分子中过渡金属与配位的硝酰基硝基氧和亚氨基硝基氧的杂旋配合物包含能量不同的交换相互作用通道,其大小和符号均不同,这已通过[Ni(B 1)( B 22 ](NO 32。一系列的混合自由基复合物可以包括具有非平凡磁性的化合物,例如[Co 2(A 1)(L 22(Piv)(MeOH)],其在3.5 K以下经历体磁有序化。
更新日期:2017-11-13
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