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Intermolecular Spin-Crossover-like Phenomenon Sensitive to Applied External Pressure in Heterospin Crystals
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.cgd.0c00240 Kseniya Maryunina 1 , Koyo Yamaguchi , Sadafumi Nishihara , Katsuya Inoue , Gleb Letyagin 1, 2 , Galina Romanenko 1 , Irina Barskaya 1 , Sergey Veber 1, 2 , Matvey Fedin 1, 2 , Artem Bogomyakov 1, 2 , Marina Petrova 1 , Vitaly Morozov 1, 2 , Victor Ovcharenko 1
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.cgd.0c00240 Kseniya Maryunina 1 , Koyo Yamaguchi , Sadafumi Nishihara , Katsuya Inoue , Gleb Letyagin 1, 2 , Galina Romanenko 1 , Irina Barskaya 1 , Sergey Veber 1, 2 , Matvey Fedin 1, 2 , Artem Bogomyakov 1, 2 , Marina Petrova 1 , Vitaly Morozov 1, 2 , Victor Ovcharenko 1
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The interaction of Cu(acF6)2 with the stable imino nitroxide 2-(pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl (ImN-mPy) at a ratio of 2:1 led to the formation of a new complex [{Cu(acF6)2}2(ImN-mPy)], which can exist in two polymorphic modifications, 1 and 2. The solid phases of both polymorphs are formed by binuclear molecules, in which the paramagnetic ligand performs the ditopic function due to the coordination of the imine N atoms of the imidazoline and pyridine heterocycles; the >N-•O fragment is not involved in coordination. The intramolecular exchange interactions in the {Cu2+-N═C–N-•O} exchange clusters were found to be ferromagnetic (JCu-R > +100 cm–1). When the cooling–heating cycles are repeated, the χT(T) dependence for 2 acquires a hysteresis with T↓ = 37 K and T↑ = 46 K due to the appearance of a strong antiferromagnetic intermolecular exchange between the >N–•O fragments of adjacent molecules. It was impossible to trace the structural changes in the solid compound at T < 50 K because the crystals cracked and lost their quality during the phase transitions. Coating the crystals with epoxide resin prevented their decomposition, but completely suppressed the spin transition. Immersion of the polymorph 2 crystals in a pressure-transmitting medium Daphne7373, which froze together with the crystals of the experimental sample at T < 200 K, also suppressed the transition to the low-spin state. An increase in the external pressure to ∼1.8 kbar led to stabilization of the strongly coupled low-spin state in the {>N–•O···O•–N <} intermolecular exchange clusters already at room temperature.
中文翻译：
分子间自旋交叉现象对杂旋晶体中施加的外压敏感
Cu（acF6）2与稳定的亚氨基亚硝基氧2-（吡啶-3-基）-4,4,5,5-四甲基-4,5-二氢-1 H-咪唑-1-氧基（ImN- m Py）以2：1的比例导致形成新的络合物[{Cu（acF6）2 } 2（ImN- m Py）]，该络合物可以两种多态性修饰形式1和2存在。两种多晶型物的固相都是由双核分子形成的，由于咪唑啉和吡啶杂环的亚胺N原子的配位，顺磁性配体具有双位官能。> N-•O片段不参与协调。{Cu 2+中的分子内交换相互作用发现-N═C–N-•O}交换簇是铁磁性的（J Cu-R > +100 cm –1）。当冷却加热循环重复时，χ Ť（Ť），用于依赖2获取具有滞后Ť ↓= 37 K和Ť ↑= 46ķ由于之间的> N-•Ø强烈的反铁磁性交换的分子间的外观相邻分子的碎片。在T处无法追踪固体化合物的结构变化<50 K，因为晶体在相变过程中破裂并失去了质量。用环氧树脂涂覆晶体可防止其分解，但完全抑制了自旋转变。将多晶型物2晶体浸入压力传递介质Daphne7373中，该晶体与实验样品的晶体在T <200 K时冻结，也抑制了向低自旋态的转变。外部压力增加到约1.8 kbar导致已经在室温下发生的{> N–O···O· –N N }}分子间交换簇中的强耦合低自旋态稳定。
更新日期：2020-04-23
中文翻译：
分子间自旋交叉现象对杂旋晶体中施加的外压敏感
Cu（acF6）2与稳定的亚氨基亚硝基氧2-（吡啶-3-基）-4,4,5,5-四甲基-4,5-二氢-1 H-咪唑-1-氧基（ImN- m Py）以2：1的比例导致形成新的络合物[{Cu（acF6）2 } 2（ImN- m Py）]，该络合物可以两种多态性修饰形式1和2存在。两种多晶型物的固相都是由双核分子形成的，由于咪唑啉和吡啶杂环的亚胺N原子的配位，顺磁性配体具有双位官能。> N-•O片段不参与协调。{Cu 2+中的分子内交换相互作用发现-N═C–N-•O}交换簇是铁磁性的（J Cu-R > +100 cm –1）。当冷却加热循环重复时，χ Ť（Ť），用于依赖2获取具有滞后Ť ↓= 37 K和Ť ↑= 46ķ由于之间的> N-•Ø强烈的反铁磁性交换的分子间的外观相邻分子的碎片。在T处无法追踪固体化合物的结构变化<50 K，因为晶体在相变过程中破裂并失去了质量。用环氧树脂涂覆晶体可防止其分解，但完全抑制了自旋转变。将多晶型物2晶体浸入压力传递介质Daphne7373中，该晶体与实验样品的晶体在T <200 K时冻结，也抑制了向低自旋态的转变。外部压力增加到约1.8 kbar导致已经在室温下发生的{> N–O···O· –N N }}分子间交换簇中的强耦合低自旋态稳定。
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