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溶剂诱导的含2,4,6-三(4-吡啶基)-1,3,5-三嗪的Co(II)配位聚合物的电子光谱和磁化率变化

Solvent-Induced Change of Electronic Spectra and Magnetic Susceptibility of Co(II) Coordination Polymer with 2,4,6-Tris(4-pyridyl)-1,3,5-triazine.

作者信息

Polunin Ruslan A, Burkovskaya Nataliya P, Satska Juliya A, Kolotilov Sergey V, Kiskin Mikhail A, Aleksandrov Grigory G, Cador Olivier, Ouahab Lahcène, Eremenko Igor L, Pavlishchuk Vitaly V

机构信息

†L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 03028, Ukraine.

‡N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 31, 119991 Moscow, GSP-1, Russian Federation.

出版信息

Inorg Chem. 2015 Jun 1;54(11):5232-8. doi: 10.1021/acs.inorgchem.5b00179. Epub 2015 May 14.

Abstract

One-dimensional coordination polymer [Co(Piv)2(4-ptz)(C2H5OH)2]n (compound 1, Piv(-) = pivalate, 4-ptz = 2,4,6-tris(4-pyridyl)-1,3,5-triazine) was synthesized by interaction of Co(II) pivalate with 4-ptz. Desolvation of 1 led to formation of [Co(Piv)2(4-ptz)]n (compound 2), which adsorbed N2 and H2 at 78 K as a typical microporous sorbent. In contrast, absorption of methanol and ethanol by 2 at 295 K led to structural transformation probably connected with coordination of these alcohols to Co(II). Formation of 2 from 1 was accompanied by change of color of sample from orange to brown and more than 2-fold decrease of molar magnetic susceptibility (χM) in the temperature range from 2 to 300 K. Resolvation of 2 by ethanol or water resulted in restoration of spectral characteristics and χM values almost to the level of that of 1. χMT versus T curves for 1 and samples, obtained by resolvation of 2 by H2O or C2H5OH, were fitted using a model for Co(II) complex with zero-field splitting of this ion.

摘要

一维配位聚合物[Co(Piv)₂(4-ptz)(C₂H₅OH)₂]ₙ(化合物1,Piv⁻ = 新戊酸根,4-ptz = 2,4,6-三(4-吡啶基)-1,3,5-三嗪)通过新戊酸钴(II)与4-ptz相互作用合成。化合物1去溶剂化后形成[Co(Piv)₂(4-ptz)]ₙ(化合物2),它作为典型的微孔吸附剂在78 K下吸附N₂和H₂。相比之下,化合物2在295 K下对甲醇和乙醇的吸附导致结构转变,这可能与这些醇与Co(II)的配位有关。从化合物1形成化合物2伴随着样品颜色从橙色变为棕色,并且在2至300 K温度范围内摩尔磁化率(χM)降低超过2倍。用乙醇或水对化合物2进行再溶剂化导致光谱特征和χM值几乎恢复到化合物1的水平。对化合物1以及通过用水或乙醇对化合物2进行再溶剂化得到的样品的χMT对T曲线,使用该离子具有零场分裂的Co(II)配合物模型进行拟合。

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