Assessing crystal field and magnetic interactions in diuranium-μ-chalcogenide triamidoamine complexes with U(IV)-E-U(IV) cores (E = S, Se, Te): implications for determining the presence or absence of actinide-actinide magnetic exchange.
Assessing crystal field and magnetic interactions in diuranium-μ-chalcogenide triamidoamine complexes with U(IV)-E-U(IV) cores (E = S, Se, Te): implications for determining the presence or absence of actinide-actinide magnetic exchange.
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DOI：
10.1039/c7sc01998j
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发表时间：
2017-09-01
期刊：
影响因子：
8.4
通讯作者：
Liddle ST
中科院分区：
文献类型：
--
作者：
Gardner BM;King DM;Tuna F;Wooles AJ;Chilton NF;Liddle ST
对UIV-E-UIV（E = S、Se、Te）复合物的分析表明，它们的行为是由于晶场效应而不是交换耦合。本文报道了一系列铀（Ⅳ）-μ-硫族化合物的合成和表征，包括它们的电子结构和磁性行为的详细研究。用Ph 3 PS、硒或碲处理[U（TrenTIPS）] [1，TrenTIPS = N（CH 2CH 2NSiPri 3）3]得到二铀（iv）-硫化物、硒化物和碲化物配合物[{U（TrenTIPS）}2（μ-E）]（E = S，2; Se，5; Te，6）。配合物2也通过用Ph 3 PS处理[U（TrenTIPS）{OP（NMe 2）3}]（3）形成，而用元素硫处理3得到二铀（iv）-过硫化物配合物[{U（TrenTIPS）}2（μ-η2：η2-S2）]（4）。配合物2-6已通过单晶X-射线衍射、NMR、IR和光学光谱、室温Evans和变温SQUID磁强计、元素分析和完整的活性空间自洽场自旋轨道计算进行了各种表征。结合的表征数据提出了一个自洽的图片的电子结构和磁性的2，5，和6，导致的结论是，单离子晶体场效应，而不是双铀磁耦合，是负责的功能，在其变温磁化数据。磁耦合的存在往往是暗示，有时量化的这些数据，因此这项研究强调了评估其他因素的重要性，如晶体场效应，可以产生类似的磁观测值，从而避免这种现象的误分配。
Analysis of UIV–E–UIV (E = S, Se, Te) complexes reveals their behaviour is due to crystal field effects and not exchange coupling. We report the synthesis and characterisation of a family of diuranium(iv)-μ-chalcogenide complexes including a detailed examination of their electronic structures and magnetic behaviours. Treatment of [U(TrenTIPS)] [1, TrenTIPS = N(CH2CH2NSiPri 3)3] with Ph3PS, selenium or tellurium affords the diuranium(iv)-sulfide, selenide, and telluride complexes [{U(TrenTIPS)}2(μ-E)] (E = S, 2; Se, 5; Te, 6). Complex 2 is also formed by treatment of [U(TrenTIPS){OP(NMe2)3}] (3) with Ph3PS, whereas treatment of 3 with elemental sulfur gives the diuranium(iv)-persulfido complex [{U(TrenTIPS)}2(μ-η2:η2-S2)] (4). Complexes 2–6 have been variously characterised by single crystal X-ray diffraction, NMR, IR, and optical spectroscopies, room temperature Evans and variable temperature SQUID magnetometry, elemental analyses, and complete active space self consistent field spin orbit calculations. The combined characterisation data present a self-consistent picture of the electronic structure and magnetism of 2, 5, and 6, leading to the conclusion that single-ion crystal field effects, and not diuranium magnetic coupling, are responsible for features in their variable-temperature magnetisation data. The presence of magnetic coupling is often implied and sometimes quantified by such data, and so this study highlights the importance of evaluating other factors, such as crystal field effects, that can produce similar magnetic observables, and to thus avoid misassignments of such phenomena.
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影响因子：
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