Reprint of "Ru(II)/Ag(I) mixed-metal complexes based on kinetically inert Ru(II) complexes with pendant binding sites as subcomponents"
Reprint of "Ru(II)/Ag(I) mixed-metal complexes based on kinetically inert Ru(II) complexes with pendant binding sites as subcomponents"
复制标题
重印“基于动力学惰性 Ru(II) 配合物（以侧链结合位点作为子成分）的 Ru(II)/Ag(I) 混合金属配合物”
DOI：
10.1016/j.poly.2015.11.010
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发表时间：
2016
期刊：
影响因子：
2.6
通讯作者：
Metherell A
中科院分区：
文献类型：
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作者：
Metherell A
合成了两种单核配合物[Ru（LoPh）_2]（PF_6）_2和fac-[Ru（L_3-Py）_3]（PF_6）_2。在[Ru（LoPh）2]（PF 6）2中，一个配体作为四齿螯合物，而另一个配体是双齿的，因此在Ru（II）配合物的核上有一个双齿的吡唑基-吡啶位点。Infac-[Ru（L3-Py）3]（PF 6）2则相反，在Ru（II）核的同一面上有三个单齿的3-吡啶基单元。两个[Ru（LoPh）2]（PF 6）2单元围绕Ag（I）离子组装得到三核[{Ru（LoPh）2}2Ag]（PF 6）5，其中Ag（I）离子为四配位。在固态下，其中三个通过π-堆积和CH = F氢键相互作用结合成三角形三聚体阵列，得到一个包含两个杯形空腔的组装体，该空腔位于中心Ag 3面的两侧，指向相反的方向;这些空腔包含H-键合的六氟磷酸根阴离子。在高浓度（11 mM）的MeCN溶液中，根据1H NMR DOSY测量，三核配合物[{Ru（LoPh）2}2Ag]（PF 6）5保持完整，但没有证据表明进一步聚集成三聚体。两个fac-[Ru（L3-Py）3]（PF 6）2单元联合收割机与两个{Ag（NCMe）}+单元和一个额外的Ag（I）离子结合，得到复杂的配位网络[{Ru（L3-Py）3}2{Ag（MeCN）2}2Ag]（PF 6）7。在该结构中，两个fac-[Ru（L3-Py）3]（PF 6）2和两个{Ag（NCMe）}+单元通过Ag-N（吡啶基）相互作用形成四核Ru 2Ag 2环，这些环通过额外的Ag-N（吡啶基）相互作用交联成一维链。然后，亲铁的Ag-Ag相互作用将所得的链连接成二维片。这两种混合金属网络都是基于动力学惰性Ru（II）络合物的初始形成，然后通过悬垂的N-供体结合位点在单独的步骤中与Ag（I）离子缔合。然而[{Ru（LoPh）2}2Ag]（PF 6）5利用π-π堆积和氢键相互作用在固态下形成包封阴离子的三聚体组装体;相反[{Ru（L3-Py）3}2{Ag（MeCN）2}2Ag]（PF 6）7利用亲银相互作用完成网络的形成。
The mononuclear complexes [Ru(LoPh)2](PF6)2andfac-[Ru(L3-Py)3](PF6)2have been prepared which contain different types of pendant binding site. In [Ru(LoPh)2](PF6)2, one ligand acts as a tetradentate chelate but the other is only bidentate such that there is one bidentate pyrazolyl-pyridine site pendant from the Ru(II) complex core. Infac-[Ru(L3-Py)3](PF6)2in contrast there are three monodentate 3-pyridyl units pendant from the same face of the Ru(II) core. Two [Ru(LoPh)2](PF6)2units assemble around an Ag(I) ion to give trinuclear [{Ru(LoPh)2}2Ag](PF6)5in which the Ag(I) ion is four coordinate. In the solid state three of these associate into a triangular trimeric array via π-stacking and CH⋯F hydrogen-bonding interactions to give an assembly which contains two cup-shaped cavities either side of a central Ag3face and pointing in opposite directions; these cavities contain H-bonded hexafluorophosphate anions. In MeCN solution at high concentrations (11 mM), according to1H NMR DOSY measurements the trinuclear complex [{Ru(LoPh)2}2Ag](PF6)5remains intact but there is no evidence for further aggregation into the trimer. Twofac-[Ru(L3-Py)3](PF6)2units combine with two {Ag(NCMe)}+units and an additional Ag(I) ion to give a complex coordination network [{Ru(L3-Py)3}2{Ag(MeCN)2}2Ag](PF6)7. In this structure twofac-[Ru(L3-Py)3](PF6)2and two {Ag(NCMe)}+units form tetranuclear Ru2Ag2rings via Ag–N(pyridyl) interactions; these rings are crosslinked into a one-dimensional chain by additional Ag–N(pyridyl) interactions. Argentophilic Ag⋯Ag interactions then connect the resulting chains into two-dimensional sheets. Both mixed-metal networks are based on initial formation of kinetically inert Ru(II) complexes which then associate in a separate step with Ag(I) ions, via pendant N-donor binding sites. However [{Ru(LoPh)2}2Ag](PF6)5exploits π–π stacking and hydrogen-bonding interactions to form in the solid state a trimeric assembly which encapsulates anions; in contrast [{Ru(L3-Py)3}2{Ag(MeCN)2}2Ag](PF6)7exploits argentophilic interactions to complete formation of the network.