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首页> 外文期刊>Chemistry: A European journal >Tuning the charge distribution and photoswitchable properties of cobalt-dioxolene complexes by using molecular techniques
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Tuning the charge distribution and photoswitchable properties of cobalt-dioxolene complexes by using molecular techniques

机译：通过分子技术调节钴-二氧戊烯配合物的电荷分布和光开关性能

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A series of cobalt complexes [Co(Me(n)tpa)(diox)]PF6 center dot sol (diox = 3,5-di-tert-butyl-1,2-dioxolene; sol = ethanol, toluene; tpa = tris(2-pyridylmethyl)amine) were prepared by using tripod-like Me(n)tpa (n = 0, 1, 2, 3), derived from tpa by successive introduction of methyl groups into the 6-position of the pyridine moieties, as an ancillary ligand. The steric hindrance induced by this substitution modulates the redox properties of the metal acceptor, thus determining the charge distribution of the metal-dioxolene moiety at room temperature. All of these complexes were characterised by using diffractometric studies, electronic spectroscopic analysis, and magnetic susceptibility measurements. In the solid state, the [Co(Me(n)tpa)(diox)](+) ions (n = 0, 1) can be described as diamagnetic cobalt (III)-catecholato derivatives, whereas a cobalt (II)-semiquinonato description seems appropriate for the paramagnetic [Co(Me(3)tpa)(diox)](+) complex. The complex [Co(Me(2)tpa)(diox)]PF6 center dot C2H5OH undergoes entropy-driven valence tautomeric interconversion at room temperature. Optically induced valence tautomerism was observed by irradiation of [Co(Me(n)tpa)-(diox)]PF6 complexes (n = 0, 1, 2) at cryogenic temperatures. The different relaxation kinetics of the photoinduced metastable phases are related to the respective free-energy changes of the interconversion, as estimated by cyclic voltammetric experiments at room temperature, and to the different lattice interactions, as supported by structural data. These results show the importance of molecular techniques for controlling the relaxation properties of photoinduced metastable species. At the same time, this behaviour strongly suggests that this paradigm exhibits intrinsic limits because of the less controllable factors that affect the process.
机译：一系列钴配合物[Co（Me（n）tpa）（diox）] PF6中心点溶胶（diox = 3,5-二叔丁基-1,2-二氧戊烯; sol =乙醇，甲苯; tpa = tris （2-吡啶基甲基）胺是通过使用三脚架状的Me（n）tpa（n = 0、1、2、3）制备的，该tpa通过连续地将甲基引入吡啶部分的6位而衍生自tpa，作为辅助配体。由该取代引起的位阻调节了金属受体的氧化还原性质，从而确定了室温下金属-二氧戊烯部分的电荷分布。所有这些配合物均通过衍射分析，电子光谱分析和磁化率测量来表征。在固态下，[Co（Me（n）tpa）（diox）]（+）离子（n = 0，1）可描述为抗磁性钴（III）-邻苯二酚衍生物，而钴（II）- semiquinonato描述似乎适用于顺磁性[Co（Me（3）tpa）（diox）]（+）络合物。复杂的[Co（Me（2）tpa）（diox）] PF6中心点C2H5OH在室温下经历熵驱动的价互变异构互变。通过在低温下照射[Co（Me（n）tpa）-（diox）] PF6配合物（n = 0，1，2）观察到光学诱导的价互变异构现象。光诱导的亚稳相的不同弛豫动力学与互变的各自自由能变化（如室温下通过循环伏安实验估算的）以及结构数据所支持的不同晶格相互作用有关。这些结果表明分子技术对于控制光诱导的亚稳态物种的弛豫特性的重要性。同时，这种行为强烈表明，由于影响过程的可控性较差，此范例显示出固有的局限性。

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