Abstract：
Anionic ancillary ligands play a critical role in the construction of rare earth (RE) metal complexes due to the large influence on the stability of the molecule and engendering emergent electronic properties that are of interest in a plethora of applications. Supporting ligands comprising oxygen donor atoms are highly pursued in RE chemistry owing to the high oxophilicity innate to these ions. The scarcely employed bis(acyl)phosphide (BAP) ligands feature oxygen coordination sites and contain a phosphide backbone rendering it attractive for RE-coordination chemistry. Here, we integrate bis(mesitoyl)phosphide (mesBAP) as an ancillary ligand into REIII chemistry to generate the first dinuclear trivalent RE complexes containing BAP ligands; [{mesBAP}2RE(THF)(μ-Cl)]2 (RE = Y, (1), Gd (2), and Dy (3); THF = tetrahydrofuran). Each RE center is ligated to two monoanionic mesBAP ligands, one THF molecule and one chloride ion. All three molecules were characterized through single-crystal X-ray diffraction, 31P NMR, IR and UV-Vis spectroscopy. 31P, 1H and 13C NMR on the diamagnetic yttrium congener 1 confirm asymmetric ligand coordination. DFT calculations conducted on 2 provided insight into the electronic structure. The magnetic properties of 2 and 3 were investigated via SQUID magnetometry. The GdIII ions exhibit weak antiferromagnetic coupling, corroborated by DFT results.
摘要：
阴离子辅助配体在稀土（RE）金属配合物的构建中起着至关重要的作用，因为它对分子的稳定性有很大的影响，并产生了大量应用中感兴趣的新兴电子特性。由于这些离子固有的高亲氧性,在RE化学中高度追求包含氧供体原子的支持配体。几乎不使用的双（酰基）磷化物（BAP）配体具有氧配位位点，并含有磷化物主链，使其对RE配位化学具有吸引力。这里,我们将双（均三甲酰基）磷化物（mesBAP）作为辅助配体整合到REIII化学中，以生成包含BAP配体的第一个双核三价RE配合物；[{mesBAP}2RE（THF）（μ-Cl）]2（RE=Y，(1),Gd(2),和Dy(3);THF=四氢呋喃)。每个RE中心连接到两个单阴离子mesBAP配体，一个THF分子和一个氯离子。所有三个分子都通过单晶X射线衍射进行了表征，31PNMR,IR和UV-Vis光谱。31P,在反磁性钇同源物1上的1H和13CNMR证实了不对称配体配位。对2进行的DFT计算提供了对电子结构的了解。通过SQUID磁力法研究了2和3的磁性。GdIII离子表现出弱的反铁磁耦合，由DFT结果证实。
