高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (3): 709.doi: 10.7503/cjcu20200475
收稿日期:
2020-07-20
出版日期:
2021-03-10
发布日期:
2021-03-08
通讯作者:
刘俊良
E-mail:liujliang5@mail.sysu.edu.cn
基金资助:
RUAN Zeyu, DU Shannan, HUANG Guozhang, TONG Mingliang, LIU Junliang()
Received:
2020-07-20
Online:
2021-03-10
Published:
2021-03-08
Contact:
LIU Junliang
E-mail:liujliang5@mail.sysu.edu.cn
摘要:
阻转异构体是一类特殊的手性化合物. 利用轴手性配体制得的具有阻转异构行为的配合物在不对称催化等领域有广泛的应用. 相比之下, 通过原位反应由非手性底物制备这类手性配合物的报道较少, 而利用非轴手性化合物原位组装得到非轴手性阻转异构体的报道则更加罕见. 乙腈是一种廉价易得的基本化工原料, 在金属离子存在下活化乙腈分子是向有机分子中引入氰甲基的一种有效手段. 本文利用乙腈分子进攻2-二吡啶基酮获得了一例含有氰甲基官能团的配体dpkMeCN-H[dpkMeCN=cyanomethyl-di(pyridin-2-yl)methanol]. 在NiII和KI的配位作用下, 该体系发生原位组装生成了一对阻转异构体. 磁性拟合结果表明镍离子之间主要为铁磁耦合, 且它们由于八面体畸变产生一定的零场分裂, 使手性镍配合物产生磁各向异性.
中图分类号:
TrendMD:
阮泽宇, 杜杉楠, 黄国璋, 童明良, 刘俊良. 原位合成手性镍配合物中的阻转异构及磁性研究. 高等学校化学学报, 2021, 42(3): 709.
RUAN Zeyu, DU Shannan, HUANG Guozhang, TONG Mingliang, LIU Junliang. Atropisomerism and Magnetic Properties of an in situ Synthesized Chiral Nickel Complex. Chem. J. Chinese Universities, 2021, 42(3): 709.
Fig.1 Conformational isomerism of dpkMeCN?H(A) and solid?state circular dichroism(CD) spectra of the powder sample for each [Ni2K] single crystal(B)(A) The conformer in the box is achiral, which is not the case in the [Ni2K] crystal structure in this work. Bottom left: the δ conformer; bottom right: the λ conformer.
Fig.2 Molecular structure of [Ni2K]The solvent molecules and hydrogen atoms are omitted for clarity. Color code: purple(K), green(Ni), grey(C), red(O), light blue(N). Left: P-atropisomer; right: M-atropisomer. The red-purple dotted line indicates the presence of electrostatic interaction between the oxygen atom and the potassium atom from the adjacent {Ni2K} motif with short distance.Symmetry codes: a. ?1/2+x, 1/2?y, ?z; b. ?3/2+x, 1/2?y, ?z; c. 1/2+x, 1/2?y, ?z.
Fig.3 Temperature dependent direct?current(DC) molar magnetic susceptibilities of [Ni2K]Inset is the filed-dependent magnetization(M vs. H) at 2 K, 3 K and 5 K. The hollow circles refer to the experimental data while the solid lines correspond to the best fits from PHI.
Fig.4 Energy level diagrams of [Ni2K]The relative energy in the figure refers to the eigenvalues obtained by the diagonalization of spin Hamiltonian. The figure shows the relative energy changes from pure spins(left) to only ferromagnetic exchange(middle), to ferromagnetic exchange and zero-field splitting(right).
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