Crystallite Tuning of Magnetic Properties in S = 1/2 Ni(III) Cyclam (Bi)sulfate Complex Salts
Crystallite Tuning of Magnetic Properties in S = 1/2 Ni(III) Cyclam (Bi)sulfate Complex Salts
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DOI：
10.1021/acs.cgd.2c01347
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发表时间：
2023-03
期刊：
影响因子：
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通讯作者：
Thomas L. Morrison;Indrani Bhowmick;M. P. Shores
中科院分区：
文献类型：
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作者：
Thomas L. Morrison;Indrani Bhowmick;M. P. Shores
配位络合物结构的分子水平晶体学调谐可以实现对控制分子内和分子间响应的小能量的操纵。近年来，对 S= 1/2 配位络合物的磁响应进行化学调谐特别受到关注，因为这些物质代表了用于开发分子量子计算机的最简单的基于电子的量子位（量子位）。在本报告中，我们讨论了新型S= 1/2 Ni(III) cyclam复合盐的晶体学调谐工具和相应的磁特性：硫酸盐桥链{[Ni(cyclam)(μ2-SO4)]ClO4·H2O}n(1)中的强反铁磁耦合以及分子[Ni(cyclam)(HSO4)2]HSO4(2)中场、温度和尺寸依赖性的慢磁弛豫。我们报道了两种操纵这些配位分子动态磁响应的方法：粒径选择和氘化。我们发现，母体化合物 2 中的磁动力学的粒子尺寸依赖性（我们将其归因于声子瓶颈效应）在氘代 2-d7 中被消除，仅揭示了更快的分子弛豫模式。
Molecular-level crystallographic tuning of a coordination complex structure can enable manipulation of the small energies that govern intra- and intermolecular responses toward molecular actuators. Chemically tuning of the magnetic response ofS= 1/2 coordination complexes is of particular interest in recent years because these species represent the simplest electron-based quantum bits (qubits) for developing molecular quantum computers. In this report, we discuss the crystallographic tuning tools and corresponding magnetic properties of novelS= 1/2 Ni(III) cyclam complex salts: strong antiferromagnetic coupling in sulfate-bridged chain {[Ni(cyclam)(μ2-SO4)]ClO4·H2O}n(1) and field-, temperature-, and size-dependent slow magnetic relaxation in molecular [Ni(cyclam)(HSO4)2]HSO4(2). We have reported two methods of manipulating the dynamic magnetic response of these coordination molecules: particle size selection and deuteration. We find that particle size dependency, which we attribute to the phonon bottleneck effect, for the magnetic dynamics in the parent compound2, is removed in deuterated2-d7, revealing only the faster molecular relaxation mode(s).