Isomer Interconversion Studied through Single-Crystal to Single-Crystal Transformations in a Metal-Organic Framework Matrix
Isomer Interconversion Studied through Single-Crystal to Single-Crystal Transformations in a Metal-Organic Framework Matrix
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DOI：
10.1021/acs.organomet.9b00401
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发表时间：
2019-09-23
期刊：
影响因子：
2.8
通讯作者：
Doonan, Christian J.
中科院分区：
文献类型：
--
作者：
Huxley, Michael T.;Young, Rosemary J.;Doonan, Christian J.
仔细改变有机金属物质的主要配位层可以改变其化学和物理性质，可能为催化提供可接近的配位位点或改变其光物理性质。在这里，我们展示了通过一系列单晶到单晶 (SC-SC) 的转变，对 Mn(CO)(3)Br 物质的主配位层进行了修饰，该物质已在合成后纳入金属有机骨架中（[Mn3L2L'] (1)，其中 L = 双(4-羧基苯基-3,5-二甲基吡唑基)-甲烷）。通过简单地改变孔溶剂化物，从而将二级配位球从极性（EtOH）改变为非极性（甲苯，THF），MOF束缚的物质从离子对转化为具有配位溴化物配体的电中性络合物。配位溶剂如乙腈和苯甲腈作为配体竞争并与 Mn(I) 中心配位。电离异构体和溶剂化异构体相互转化的证明使得可以制备容易进行阴离子交换的材料，在溴化物保持不配位的情况下，或者当溴化物与MOF束缚的Mn-羰基物质配位时，会产生光谱红移的电荷中性物质，为光诱导CO释放提供潜在的较低能量的光解作用。
Careful changes to the primary coordination sphere of an organometallic species can modify its chemical and physical properties, potentially providing accessible coordinating sites for catalysis or modifying its photophysical properties. Here we show, via a series of single-crystal to single-crystal (SC-SC) transformations, the modification of the primary coordination sphere of a Mn(CO)(3)Br species that has been postsynthetically incorporated into a metal-organic framework ([Mn3L2L'] (1), where L = bis(4-carboxyphenyl-3,5-dimethylpyrazolyl)-methane). By simply changing the pore solvates, and hence the secondary coordination sphere from polar (EtOH) to nonpolar (toluene, THF), the MOF-tethered species is converted from an ion pair to a charge-neutral complex with a coordinated bromide ligand. Coordinating solvents such as acetonitrile and benzonitrile compete as ligands and coordinate to the Mn(I) center. The demonstration of interconversion of ionization and solvation isomers allows the preparation of materials for facile anion exchange, in the cases where bromide remains uncoordinated, or when the bromide is coordinated to the MOF-tethered Mn-carbonyl species, a charge-neutral species is generated whose spectrum is red-shifted, offering potentially lower energy photolysis for photoinduced CO release.