Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (Cp*2Cr+)(H+)(H2TPCor・2-)・C6H4Cl2
Solid state structures and properties of free-base 5,10,15-triphenylcorrole (TPCor) anions obtained by deprotonation and reduction. Effective magnetic coupling of spins in (Cp*2Cr+)(H+)(H2TPCor・2-)・C6H4Cl2
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通过去质子化和还原获得的游离碱 5,10,15-三苯基咯咯 (TPCor) 阴离子的固态结构和性质 (Cp*2Cr+)(H+)(H2TPCor·2-)·C6H4Cl2 中自旋的有效磁耦合。
DOI：
10.1039/c7dt02901b
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发表时间：
2017
期刊：
影响因子：
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通讯作者：
Lyubovskaya Rimma N.
中科院分区：
文献类型：
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作者：
Konarev Dmitri V.;Karimov Dmitri R.;Khasanov Salavat S.;Shestakov Alexander F.;Otsuka Akihiro;Yamochi Hideki;Kitagawa Hiroshi;Lyubovskaya Rimma N.
用十甲基二茂铬还原5，10，15-三苯基咔咯（H3 TPC或）得到（Cp*2Cr+）（H+）（H2 TPC或stec 2−）·C6 H4 Cl 2（1）。它伴随着H3 TPC或的去质子化和平面H2 TPC或stec 2−自由基二价阴离子的形成。配合物1在H2 TArylCor stec 2−的溶液光谱中观察到约750 nm处的谱带，并显示归因于还原的咔咯大环的EPR信号。1在300 K时的磁矩为4.10μB，表明Cp*2Cr+（S = 3/2）和H2 TPC或stec 2−（S = 1/2）的贡献。这些顺磁物质在π堆叠中交替出现，在韦斯温度为−31 K时提供了相当有效的反铁磁自旋耦合。为了区分H2 TPC stec 2−二价阴离子和去质子化的H2 TPC or −阴离子，我们还研究了{cryptand[2，2，2]（Na+）}（H2 TPC or −）·0.5C6H4Cl2（2）与去质子化的咔咯阴离子的盐。在这种情况下，也形成平面大环。然而，2中的H2 TPC或−的性质不同于1中的H2 TPC或stec 2−。
The reduction of 5,10,15-triphenylcorrole (H3TPCor) with decamethylchromocene yields (Cp*2Cr+)(H+)(H2TPCor˙2−)·C6H4Cl2 (1). It is accompanied by the deprotonation of H3TPCor and the formation of planar H2TPCor˙2− radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of H2TArylCor˙2− and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10μB at 300 K indicates the contribution of Cp*2Cr+ (S = 3/2) and H2TPCor˙2− (S = 1/2). These paramagnetic species alternate in the π-stacks providing rather effective antiferromagnetic coupling of spins at the Weiss temperature of −31 K. To distinguish the H2TPC˙2− dianions from the deprotonated H2TPCor− anions, we also studied the {cryptand[2,2,2](Na+)}(H2TPCor−)·0.5C6H4Cl2 (2) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of H2TPCor− in 2 differ from those of H2TPCor˙2− in 1.