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首页> 外文期刊>Chemistry: A European journal >Simultaneous Presence of Both Open Metal Sites and Free Functional Organic Sites in a Noncentrosymmetric Dynamic Metal-Organic Framework with Bimodal Catalytic and Sensing Activities
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Simultaneous Presence of Both Open Metal Sites and Free Functional Organic Sites in a Noncentrosymmetric Dynamic Metal-Organic Framework with Bimodal Catalytic and Sensing Activities

机译：具有双峰催化和传感活性的非中心对称动态金属有机骨架中同时存在开放金属位点和自由功能有机位点

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摘要

Assimilation of open metal sites (OMSs) and free functional organic sites (FOSs) with a framework strut has opened up a new route for the fabrication of novel metal-organic materials, thereby providing a unique opportunity to explore their multiple functionalities. A new metal-organic framework (MOF), {[Cu(ina)_2(H_2O)] [Cu(ina)_2(bipy)]·_2H_2O}_n (1) (ina=isonicotinate, bipy=4,4'-bipyridine), has been synthesized and characterized. Complex 1 is crystallized in the orthorhombic noncentrosymmetric space group Aba2 and consists of two different 2D coordination polymers, [Cu-(ina)_2(H_2O)]_n and [Cu(ina)_2(bipy)]_n, with entrapped solvent water molecules. Hydrogen-bonding interactions assemble these two different 2D coordination layers in a single-crystal structure with interdigitation of pendant 4,4'-bipy from one layer into the groove of another. Upon removal of guest molecules, 1 undergoes a structural transformation in single-crystal-tosingle-crystal fashion with expansion of the effective void space. Each metal center is five-coordinated and thus can potentially behave as an OMS, and the free pyridyl groups of pendant 4,4'-bipy moieties and free-C=O groups can act as free FOSs. Thus, owing to presence of both OMSs and free FOSs, the framework exhibits multifunctional properties. Owing to the presence of OMSs, the framework can act as a Lewis acid catalyst as well as a smallmolecule sensor material, and in a similar way, owing to the presence of free FOSs, it performs as a Lewis base catalyst and a cation sensor material. Furthermore, owing to noncentrosymmetry with large polarity along a particular direction, it shows strong second-harmonic generationonlinear optical (SHG-NLO) activity.
机译：带有框架撑杆的开放金属位点（OMS）和自由功能有机位点（FOS）的吸收开辟了制造新型金属有机材料的新途径，从而为探索其多种功能提供了独特的机会。一种新的金属有机骨架（MOF），{[Cu（ina）_2（H_2O）] [Cu（ina）_2（bipy）]·_2H_2O} _n（1）（ina = isonicotinate，bipy = 4,4'-联吡啶），已经合成并表征。配合物1在正交各向异性非中心对称空间群Aba2中结晶，并且由两种不同的2D配位聚合物[Cu-（ina）_2（H_2O）] _ n和[Cu（ina）_2（bipy）] _ n组成，并带有溶剂水分子。氢键相互作用将这两个不同的2D配位层组装成一个单晶结构，其中4,4'-bipy侧链从一层到另一层的凹槽相互交错。除去客体分子后，1会以单晶-单晶的方式进行结构转变，并扩展有效空隙空间。每个金属中心是五个配位的，因此可以潜在地充当OMS，并且4,4'-联吡啶侧基的游离吡啶基和游离C = O基团可以充当游离FOS。因此，由于同时存在OMS和自由FOS，因此该框架具有多功能特性。由于存在OMS，该骨架可以充当路易斯酸催化剂以及小分子传感器材料，并且由于存在游离的FOS，其以类似的方式充当路易斯碱催化剂和阳离子传感器材料。此外，由于沿特定方向具有大极性的非中心对称性，它显示出强大的二次谐波生成/非线性光学（SHG-NLO）活性。

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