Synthesis and characterization of carbene derivatives of Th@C (3v)(8)-C(82) and U@C (2v)(9)-C(82): exceptional chemical properties induced by strong actinide-carbon cage interaction.
Synthesis and characterization of carbene derivatives of Th@C (3v)(8)-C(82) and U@C (2v)(9)-C(82): exceptional chemical properties induced by strong actinide-carbon cage interaction.
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Th@C3v(8)-C82和U@C2v(9)-C82卡宾衍生物的合成和表征：强锕系元素与碳笼相互作用诱导的特殊化学性质
DOI：
10.1039/d0sc06111e
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发表时间：
2020-12-21
期刊：
影响因子：
8.4
通讯作者：
Chen N
中科院分区：
文献类型：
--
作者：
Liu X;Li B;Yang W;Yao YR;Yang L;Zhuang J;Li X;Jin P;Chen N
内嵌金属富勒烯（EMF）的化学功能化是这些新型碳材料应用的关键。锕系元素EMF是EMF家族的新成员，具有独特的分子和电子结构，但其化学性质尚未得到研究。本文首次报道了锕系元素EMF的化学功能化，系统研究了Th@C3v（8）-C82和U@C2v（9）-C82与2-金刚烷-2，3 ′-[3 H]-二氮杂环丙烷（AdN 2，1）的光化学反应。结合HPLC和MALDI-TOF分析表明，通过光化学反应的卡宾加成得到Th@C3v（8）-C82 Ad的三种异构体和U@C2v（9）-C82 Ad的四种异构体（Ad =金刚烷叉基），表现出比它们的镧系类似物显著更高的反应性。在这些新的EMF衍生物中，Th@C3v（8）-C82 Ad（I，II，III）和U@C2v（9）-C82 Ad（I，II，III）被成功地分离并通过UV-vis-NIR光谱进行表征。特别地，第一锕系富勒烯衍生物Th@C3v（8）-C82 Ad（I）和U@C2v（9）-C82 Ad（I）的分子结构通过单晶X射线晶体学明确地确定，两者都显示出[6，6]-开笼结构。此外，在室温下观察到Th@C3v（8）-C82 Ad（II）、Th@C3v（8）-C82 Ad（III）、U@C2v（9）-C82 Ad（II）和U@C2v（9）-C82 Ad（III）的异构化。计算研究表明，Th@C3v（8）-C82 Ad（I）和U@C2v（9）-C82 Ad（I）的笼上连接的碳原子具有最大的负电荷，从而促进亲电攻击。此外，它揭示了，与它们的镧系类似物相比，Th@C3v（8）-C82和U@C2v（9）-C82具有更近的金属笼距离，增加的金属到笼的电荷转移，以及源自扩展的Th-5 f和U-5 f轨道对占据的分子轨道的显著贡献的强的金属-笼相互作用，所有这些都导致它们不寻常的高反应性。这项研究提供了第一次洞察特殊的化学性质的锕系元素内嵌富勒烯，这为未来的功能化和应用这些新的EMF化合物铺平了道路。
Chemical functionalization of endohedral metallofullerenes (EMFs) is essential for the application of these novel carbon materials. Actinide EMFs, a new EMF family member, have presented unique molecular and electronic structures but their chemical properties remain unexplored. Here, for the first time, we report the chemical functionalization of actinide EMFs, in which the photochemical reaction of Th@C3v(8)-C82 and U@C2v(9)-C82 with 2-adamantane-2,3′-[3H]-diazirine (AdN2, 1) was systematically investigated. The combined HPLC and MALDI-TOF analyses show that carbene addition by photochemical reaction afforded three isomers of Th@C3v(8)-C82Ad and four isomers of U@C2v(9)-C82Ad (Ad = adamantylidene), presenting notably higher reactivity than their lanthanide analogs. Among these novel EMF derivatives, Th@C3v(8)-C82Ad(I, II, III) and U@C2v(9)-C82Ad(I, II, III) were successfully isolated and were characterized by UV-vis-NIR spectroscopy. In particular, the molecular structures of first actinide fullerene derivatives, Th@C3v(8)-C82Ad(I) and U@C2v(9)-C82Ad(I), were unambiguously determined by single crystal X-ray crystallography, both of which show a [6,6]-open cage structure. In addition, isomerization of Th@C3v(8)-C82Ad(II), Th@C3v(8)-C82Ad(III), U@C2v(9)-C82Ad(II) and U@C2v(9)-C82Ad(III) was observed at room temperature. Computational studies suggest that the attached carbon atoms on the cages of both Th@C3v(8)-C82Ad(I) and U@C2v(9)-C82Ad(I) have the largest negative charges, thus facilitating the electrophilic attack. Furthermore, it reveals that, compared to their lanthanide analogs, Th@C3v(8)-C82 and U@C2v(9)-C82 have much closer metal–cage distance, increased metal-to-cage charge transfer, and strong metal–cage interactions stemming from the significant contribution of extended Th-5f and U-5f orbitals to the occupied molecular orbitals, all of which give rise to their unusual high reactivity. This study provides first insights into the exceptional chemical properties of actinide endohedral fullerenes, which pave ways for the future functionalization and application of these novel EMF compounds.
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影响因子：
8.4
作者：
Cai W;Morales-Martínez R;Zhang X;Najera D;Romero EL;Metta-Magaña A;Rodríguez-Fortea A;Fortier S;Chen N;Poblet JM;Echegoyen L
通讯作者：
Echegoyen L
影响因子：
2.2
作者：
Jin, Peng;Liu, Chang;Zhao, Yujun
通讯作者：
Zhao, Yujun
影响因子：
2.2
作者：
Li, Ying;Yang, Le;Jin, Peng
通讯作者：
Jin, Peng
影响因子：
15
作者：
Lu, Xing;Nikawa, Hidefumi;Nagase, Shigeru
通讯作者：
Nagase, Shigeru
影响因子：
1.7
作者：
BERGNER, A;DOLG, M;PREUSS, H
通讯作者：
PREUSS, H