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首页> 外文期刊>Faraday discussions >Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism
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Photoswitchable stable charge-distributed states in a new cobalt complex exhibiting photo-induced valence tautomerism

机译：新型钴络合物中的光开关稳定电荷分布态，其表现出光致价互变异构

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We report the synthesis and magnetic and photomagnetic behaviour of a novel valence tautomeric cobalt complex, [Co(3,5-dbbq)(2)(mu-bpym)] (1) (3,5-dbbq = 3,5-di-tert-butyl-1,2-benzoquinone and mu-bpym = 2,2'-bipyrimidine). The synthesis is performed by reacting Co-2(CO)(8) and mu-bpym in the presence of the ligand 3,5-dbbq in a mixed solvent under inert atmosphere. The magnetic behavior clearly shows the presence of electron transfer from the catecholate ligand to the cobalt center, producing valence tautomers of [Co-II(SQ)(2)] with a transition temperature (T-1/2) of 215 K. Photomagnetic studies, performed via both SQUID magnetometry and X-band electron paramagnetic resonance, show the clear presence of photoinduced valence tautomerism, at temperatures considerably higher than previous systems. A metastable charge distribution is observed, strengthening previous investigations on the character of mixed valence ligands. Entropy-driven valence tautomeric interconversion is observed, and drives the transition to the most stable charge distribution. The complex has the ability to coordinate and can be used as a photoswitchable building block, with the photomagnetic characterisation evidencing a metastable state lifetime of the photoinduced valence tautomeric process of ca. 2.9 x 10(4) s below 20 K. The observed yields are higher than ones in similar systems, showing that tiny changes in the molecular structures may have a huge impact.
机译：我们报告了新型价互变异构钴配合物[Co（3,5-dbbq）（2）（mu-bpym）]（1）（3,5-dbbq = 3,5-di -叔丁基-1,2-苯醌和mu-bpym = 2,2'-联嘧啶）。通过在惰性气氛下在混合溶剂中在配体3,5-dbbq存在下，使Co-2（CO）（8）与mu-bpym反应，进行合成。磁性行为清楚地表明了从儿茶酚酸配体到钴中心的电子转移，产生了[Co-II（SQ）（2）]的价互变异构体，其转变温度（T-1 / 2）为215K。通过SQUID磁力测定法和X波段电子顺磁共振进行的研究表明，在比以前的系统温度高得多的温度下，明显存在光诱导价互变异构现象。观察到亚稳的电荷分布，加强了先前对混合价配体特征的研究。观察到熵驱动的价互变异构互变，并驱动过渡到最稳定的电荷分布。该配合物具有配位能力，可用作光可开关的构建基块，其光磁特性证明了ca的光诱导价互变异构过程的亚稳态状态寿命。在20 K以下时为2.9 x 10（4）s。观察到的产率高于类似系统中的产率，这表明分子结构的微小变化可能会产生巨大影响。

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