Konarev Dmitri V, Khasanov Salavat S, Otsuka Akihiro, Ishikawa Manabu, Yamochi Hideki, Saito Gunzi, Lyubovskaya Rimma N
Institute of Problems of Chemical Physics RAS , Chernogolovka, 142432, Russia.
Inorg Chem. 2014 Jul 7;53(13):6850-5. doi: 10.1021/ic500689n. Epub 2014 Jun 19.
Fullerene salt {(Ph3P)3Au(+)}2(C60(•-))2(C60)·C6H4Cl2 (1) containing (Ph3P)3Au(+) cations with the C3v symmetry has been obtained as single crystals. Hexagonal corrugated fullerene layers formed in 1 alternate with the layers consisting of (Ph3P)3Au(+) and C6H4Cl2 along the c axis. According to IR spectra and peculiarities of the crystal structure, the charge on fullerenes in the layers is evaluated to be -1 for two and close to zero for one C60. These fullerenes have different cationic surroundings, and positively charged gold atoms approach closer to C60(•-). Charged and neutral fullerenes are closely packed within hexagonal layers with an interfullerene center-to-center distance of 10.02 Å and multiple short van der Waals C···C contacts. The distances between C60(•-) are essentially longer with an interfullerene center-to-center distance of 10.37 Å due to corrugation of the layers, and no van der Waals contacts are formed in this case. As a result, each C60(•-) has only three negatively charged fullerene neighbors with rather long interfullerene distances providing only weak antiferromagnetic interaction of spins in the fullerene layers with a Weiss temperature of -5 K.
已获得含有具有(C_{3v})对称性的((Ph_3P)3Au(+))阳离子的富勒烯盐({(Ph_3P)3Au(+)}2(C{60}(•-))2(C{60})\cdot C_6H_4Cl_2)（1）的单晶。在1中形成的六边形波纹状富勒烯层与沿着(c)轴由((Ph_3P)3Au(+))和(C_6H_4Cl_2)组成的层交替排列。根据红外光谱和晶体结构的特点，层中富勒烯上的电荷对于两个(C{60})评估为(-1)，对于一个(C{60})接近零。这些富勒烯具有不同的阳离子环境，带正电的金原子更接近(C{60}(•-))。带电和中性富勒烯在六边形层内紧密堆积，富勒烯中心到中心的距离为(10.02 Å)，并且有多个短的范德华(C···C)接触。由于层的波纹状，(C_{60}(•-))之间的距离本质上更长，富勒烯中心到中心的距离为(10.37 Å)，在这种情况下没有形成范德华接触。结果，每个(C_{60}(•-))只有三个带负电的富勒烯邻居，富勒烯间距离相当长，仅提供富勒烯层中自旋的弱反铁磁相互作用，魏斯温度为(-5 K)。
