Konarev Dmitri V, Karimov Dmitri R, Khasanov Salavat S, Shestakov Alexander F, Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Lyubovskaya Rimma N
Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 Russia.
Dalton Trans. 2017 Oct 17;46(40):13994-14001. doi: 10.1039/c7dt02901b.
The reduction of 5,10,15-triphenylcorrole (HTPCor) with decamethylchromocene yields (CpCr)(H)(HTPCor˙)·CHCl (1). It is accompanied by the deprotonation of HTPCor and the formation of planar HTPCor˙ radical dianions. Complex 1 manifests a band at about 750 nm observed in the solution spectra of HTArylCor˙ and demonstrates an EPR signal attributed to the reduced corrole macrocycle. The magnetic moment of 1 of 4.10μ at 300 K indicates the contribution of CpCr (S = 3/2) and HTPCor˙ (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 HTPC˙ dianions from the deprotonated HTPCor anions, we also studied the {cryptand2,2,2}(HTPCor)·0.5CHCl (2) salt with deprotonated corrole anions. In this case, a planar macrocycle was formed as well. However, the properties of HTPCor in 2 differ from those of HTPCor˙ in 1.
用十甲基二茂铬还原5,10,15-三苯基卟啉（HTPCor）得到（CpCr）（H）（HTPCor˙）·CHCl（1）。这一过程伴随着HTPCor的去质子化以及平面型HTPCor˙自由基二价阴离子的形成。配合物1在HTArylCor˙的溶液光谱中约750 nm处出现一个吸收带，并显示出一个归属于还原卟啉大环的电子顺磁共振信号。1在300 K时的磁矩为4.10μ，表明CpCr（S = 3/2）和HTPCor˙（S = 1/2）的贡献。这些顺磁物种在π堆积中交替排列，在-31 K的魏斯温度下提供了相当有效的自旋反铁磁耦合。为了区分HTPC˙二价阴离子和去质子化的HTPCor阴离子，我们还研究了含有去质子化卟啉阴离子的{穴醚2,2,2}(HTPCor)·0.5CHCl（2）盐。在这种情况下，也形成了一个平面大环。然而，2中HTPCor的性质与1中HTPCor˙的性质不同。
