Revisiting cobaloxime(II) chemistry and clearing misconceptions of cobaloxime(II) in diamagnetic Ni(II) and Pd(II) matrix by comprehensive magnetic measurements

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-04-15 DOI:10.1039/d5cp00629e

Yukina Suzuki, Mirosław Arczyński, Masanori Wakizaka, Hisaaki Tanaka, Ryuta Ishikawa, Takefumi Yoshida, Takeshi Yamane, Kazunobu Sato, Ryota Sakamoto, Masahiro Yamashita

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Abstract

Co(II) was doped into the diamagnetic one-dimensional framework of bis(dimethylglyoximato) Ni(II) and Pd(II) complex [Ni/Pd^II(Hdmg)₂] (Hdmg = dimethylglyoximate anion) (hereafter referred to as Co@Ni and Co@Pd samples) to study magnetic properties as a potential spin qubit. The previous report of electron paramagnetic resonance (EPR) spectroscopy of this compound prepared using the same doping strategy in the Ni matrix observed a spectrum assigned to S = 1/2 Co(II) with g_x = 2.58, g_y = 2.26 g_x = 1.98. The relatively large g_x value, compared to those typically observed in [Co(Hdmg)2Bx] complexes (B = Lewis base ligand, x = 1 or 2), which fall within the ranges g_x = 2.1 - 2.4, g_y = 2.0 - 2.2 and g_z ≈ 2.01, led to the interpretation of this species as Co(Hdmg)2 with an extremely axial interaction. However, our EPR analysis, combined with SQUID (superconducting quantum interference device) and XANES (X-ray absorption near-edge structure) analysis, revealed that the previously identified species are μ-O bridged dimers: [Co(Hdmg)(μ-Hdmg)]2 and [Co(Hdmg)(μ-Hdmg)][Ni/Pd(Hdmg)(μ-Hdmg)]. Furthermore, our liquid-helium temperature EPR spectra revealed a Co species with much greater axial g anisotropy (g_x = 4.75 g_y,z ≈ 0.75 for Co@Ni and g_x = 4.2 g_y,z ≈ 1.33 for Co@Pd). We assign this species to the truly planar Co(Hdmg)₂ with negligibly weak axial interaction, which might have been overlooked in the previous EPR studies.

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通过综合磁性测量重温钴肟(II)化学并澄清二磁性镍(II)和钯(II)基体中钴肟(II)的误解

将Co（II）掺杂到双（二甲基乙氧基肟酸酯）Ni（II）和Pd（II）配合物[Ni/PdII(Hdmg)2] （Hdmg =二甲基乙氧基肟酸阴离子）（以下简称Co@Ni和Co@Pd样品）的抗磁性一维框架中，研究其作为潜在自旋量子比特的磁性。在Ni基体中采用相同的掺杂策略制备的该化合物的电子顺磁共振（EPR）谱图中，观察到光谱分配为S = 1/2 Co(II), gx = 2.58, gy = 2.26, gx = 1.98。与在[Co(Hdmg)2Bx]配合物（B = Lewis碱配体，x = 1或2）中观察到的典型gx值相比，相对较大的gx值落在gx = 2.1 - 2.4, gy = 2.0 - 2.2和gz≈2.01的范围内，导致该物种被解释为具有极轴向相互作用的Co(Hdmg)2。然而，我们的EPR分析结合SQUID（超导量子干涉装置）和XANES （x射线吸收近边结构）分析显示，先前鉴定的物质是μ-O桥接二聚体：[Co(Hdmg)(μ-Hdmg)]2和[Co(Hdmg)(μ-Hdmg)][Ni/Pd(Hdmg)(μ-Hdmg)]。此外，我们的液氦温度EPR光谱显示Co物质具有更大的轴向g各向异性（gx = 4.75 gy,z≈0.75 Co@Ni和gx = 4.2 gy,z≈1.33 Co@Pd）。我们认为这个物种是真正平面的Co(Hdmg)2，具有可忽略的弱轴向相互作用，这在以前的EPR研究中可能被忽略了。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.