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Antiferromagnetic Exchange and Metal–Metal Bonding in Roussin’s Black Sulfur and Selenium Salts
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-18 , DOI: 10.1021/acs.inorgchem.1c02052 Daniel J SantaLucia 1 , John F Berry 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-18 , DOI: 10.1021/acs.inorgchem.1c02052 Daniel J SantaLucia 1 , John F Berry 1
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Atom-efficient syntheses of the tetraethylammonium Roussin black sulfur and selenium salts ((Et4N)[Fe4E3(NO)7], E = S, Se) as well as their 15N-labeled counterparts are described herein. Broken-symmetry DFT calculations were conducted on both complexes to model an antiferromagnetic interaction between the apical {FeNO}7 unit, Sap = 3/2, and the three basal {Fe(NO)2}9 units, Sbas = 1/2. The calculated J values are −1813 and −1467 cm–1 for the sulfur and selenium compounds, respectively. The mechanism for antiferromagnetic exchange in both compounds was deduced to be direct exchange on the basis of the partially overlapping magnetic orbitals with orbital density only residing on the Fe-centers. The obtained Mössbauer parameters are most consistent with the calculated MS = 0 broken-symmetry state for both complexes. The values for J have been determined with variable-temperature 15N NMR experiments. Values of −1660 and −1430 cm–1 for the sulfur and selenium compounds, respectively, were obtained by fits to the variable-temperature NMR data, further validating the broken-symmetry MS = 0 model of the electronic structure.
中文翻译：
Roussin 黑硫和硒盐中的反铁磁交换和金属-金属键合
本文描述了四乙基铵 Roussin 黑硫和硒盐（(Et 4 N)[Fe 4 E 3 (NO) 7 ]，E = S，Se）及其15 N 标记的对应物的原子效率合成。对两种配合物进行了破坏对称 DFT 计算，以模拟顶端 {FeNO} 7单元S ap = 3/2 和三个基底 {Fe(NO) 2 } 9单元S bas = 1/之间的反铁磁相互作用2. 计算出的J值为 −1813 和 −1467 cm –1分别为硫和硒化合物。基于轨道密度仅位于 Fe 中心的部分重叠的磁轨道，这两种化合物的反铁磁交换机制被推断为直接交换。获得的穆斯堡尔参数与计算出的两种复合物的M S = 0 破坏对称状态最一致。J的值是通过变温15 N NMR 实验确定的。硫和硒化合物的 -1660 和 -1430 cm –1值分别是通过拟合变温 NMR 数据获得的，进一步验证了破坏对称性M S = 0 电子结构模型。
更新日期：2021-11-01
中文翻译：
Roussin 黑硫和硒盐中的反铁磁交换和金属-金属键合
本文描述了四乙基铵 Roussin 黑硫和硒盐（(Et 4 N)[Fe 4 E 3 (NO) 7 ]，E = S，Se）及其15 N 标记的对应物的原子效率合成。对两种配合物进行了破坏对称 DFT 计算，以模拟顶端 {FeNO} 7单元S ap = 3/2 和三个基底 {Fe(NO) 2 } 9单元S bas = 1/之间的反铁磁相互作用2. 计算出的J值为 −1813 和 −1467 cm –1分别为硫和硒化合物。基于轨道密度仅位于 Fe 中心的部分重叠的磁轨道，这两种化合物的反铁磁交换机制被推断为直接交换。获得的穆斯堡尔参数与计算出的两种复合物的M S = 0 破坏对称状态最一致。J的值是通过变温15 N NMR 实验确定的。硫和硒化合物的 -1660 和 -1430 cm –1值分别是通过拟合变温 NMR 数据获得的，进一步验证了破坏对称性M S = 0 电子结构模型。
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