Heterometallic coordination polymers incorporating dipyrrin based heteroleptic copper and cobalt complexes: to Ag-π or not?
Heterometallic coordination polymers incorporating dipyrrin based heteroleptic copper and cobalt complexes: to Ag-π or not?
复制标题
包含二吡啉基杂配铜和钴配合物的异金属配位聚合物：是否为 Ag-π？
作者：
Antoine Béziau;Stéphane A. Baudron;M. W. Hosseini
使用基于乙酰丙酮或附加有吡啶基的二吡咯部分的配体，合成了一系列新颖的混合配位的铜（II）和钴（III）配合物，（acacpy（2））Cu（dpm-py）和合成了（acacpy（2））Co（dpm-py）（2）（acacpy（2）= 1，3-双（4-吡啶基）-1，3-丙二酸盐; dpm-py = 5-（4-吡啶基）二吡咯）配合物，并对其进行了表征。这两个配合物是dpm-py与（acacpy（2））M均配体（M = Cu（II），Co（II））反应得到的。在固态下，（acacpy（2））Cu（dpm-py）配合物表现为自互补金属配体，通过外围吡啶基与铜中心配位形成一维配位聚合物（CP）.相比之下，具有配位饱和Co（III）中心的八面体（acacpy（2））Co（dpm-py）（2）络合物结晶为孤立的单核物种。为了产生异金属CP，两种络合物在与不同的银（I）盐组合时被用作金属配体。（acacpy（2））Cu（dpm-py）与Ag（BF（4））或Ag（TfO）反应后，分别得到二维和三维异金属网络。在这两种情况下，观察到由三个外围吡啶基结合Ag（+）阳离子导致的片型排列。这些2D片层通过Ag-π相互作用与吡咯环进一步互连。在相同条件下，（acacpy（2））Co（dpm-py）（2）与Ag（TfO）的结合导致两种网络的连接模式和维数不同。有趣的是，尽管在2D网络中没有观察到Ag-π相互作用，但在1D结构中检测到与吡啶基部分的配位键合和Ag-π相互作用的组合。
Using ligands based on either an acetylacetonate or a dipyrrin moiety appended with pyridyl groups, a series of novel heteroleptic copper(II) and cobalt(III) complexes combining both chelate units such as (acacpy(2))Cu(dpm-py) and (acacpy(2))Co(dpm-py)(2) (acacpy(2) = 1,3-bis(4-pyridyl)-1,3-propanedionate; dpm-py = 5-(4-pyridyl)dipyrrin) have been prepared and fully characterized. These two complexes were obtained upon reaction of dpm-py with the (acacpy(2))M homoleptic species (M = Cu(II), Co(II)). In the solid state, the (acacpy(2))Cu(dpm-py) complex behaves as a self-complementary metallatecton and leads to the formation of a 1D coordination polymer (CP) through the coordination of a peripheral pyridyl group to the copper centre. Contrastingly, the octahedral (acacpy(2))Co(dpm-py)(2) complex featuring a coordinatively saturated Co(III) centre crystallizes as an isolated mononuclear species. In order to generate heterometallic CPs, both complexes have been used as metallatectons upon their combination with different silver(I) salts. Upon reaction of (acacpy(2))Cu(dpm-py) with Ag(BF(4)) or Ag(TfO), 2- and 3-D heterometallic networks were obtained, respectively. In both cases, sheet type arrangements resulting from the binding of Ag(+) cations by three peripheral pyridyl groups were observed. These 2D sheets are further interconnected through Ag-π interactions with the pyrrolic rings. Under the same conditions, the combination of (acacpy(2))Co(dpm-py)(2) with Ag(TfO) leads to two networks differing by their connectivity patterns and dimensionality. Interestingly, whereas no Ag-π interactions were observed for the 2D network, a combination of coordination bonding with the pyridyl moieties and Ag-π interactions was detected for the 1D architecture.
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DOI：
10.1002/chin.200029102
发表时间：
2000-03
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Dorota Gryko;J. Lindsey
通讯作者：
Dorota Gryko;J. Lindsey
影响因子：
4.6
作者：
J. R. Stork;Van S Thoi;Seth M. Cohen
通讯作者：
J. R. Stork;Van S Thoi;Seth M. Cohen
影响因子：
15
作者：
Halper, Sara R.;Do, Loi;Cohen, Seth M.
通讯作者：
Cohen, Seth M.
影响因子：
4.9
作者：
Garibay, Sergio J.;Stork, Jay R.;Telfer, Shane G.
通讯作者：
Telfer, Shane G.