Lu Xiao-Qin, Zhao Xiao-Ni, Mu Yue-Wen, Li Si-Dian
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Shanxi Center for Testing of Functional Agro-Products, Shanxi Agricultural University, Taiyuan 030031, China.
Phys Chem Chem Phys. 2022 Sep 14;24(35):21078-21084. doi: 10.1039/d2cp03142f.
Extensive global minimum searches augmented with first-principles theory calculations performed in this work indicate that the experimentally observed perfect inverse sandwich lanthanide boride complexes LaB (1), LaB (3), LaB (7) can be extended to their actinide counterparts AcB (1'), AcB (3'), AcB (7') with a B monocyclic ring ( = 7-9) sandwiched by two Ac dopants. Such MB inverse sandwiches (1/1', 3/3', 7/7') can be used as building blocks to generate the ground-state LaB (2)/AcB (2'), LaB (4)/AcB (4'), / LaB (5)/AcB (5'), AcB (6'), AcB, AcB (8'), LaB (9)/AcB (9'), and AcB (10') which are based on boron frameworks consisting of multiple conjoined B rings ( = 7-9). Detailed bonding analyses show that effective (d-p)σ, (d-p)π and (d-p)δ coordination bonds are formed between the B rings and metal doping centers, conferring three-dimensional aromaticity and extra stability to the systems. In particular, the perfect body-centered cubic AcB (6') and AcB with six conjoined B rings can be extended in , , and dimensions to form one-dimensional AcB (11'), two-dimensional AcB (12'), and three-dimensional AcB (13') nanomaterials, presenting a B-based bottom-up approach from metal boride nanoclusters to their low-dimensional nanomaterials.
在本工作中进行的广泛的全局最小搜索以及基于第一性原理理论的计算表明，实验观察到的完美反夹心镧系硼化物配合物LaB(1)、LaB(3)、LaB(7)可以扩展到它们的锕系对应物AcB(1')、AcB(3')、AcB(7')，其中一个B单环（= 7 - 9）夹在两个Ac掺杂剂之间。这种MB反夹心结构（1/1'﹑3/3'﹑7/7'）可用作构建基元，以生成基态的LaB(2)/AcB(2')、LaB(4)/AcB(4')、LaB(5)/AcB(5')、AcB(6')、AcB、AcB(8')、LaB(9)/AcB(9')和AcB(10')，它们基于由多个相连的B环（= 7 - 9）组成的硼骨架。详细的键合分析表明，B环与金属掺杂中心之间形成了有效的(d - p)σ、(d - p)π和(d - p)δ配位键，赋予了体系三维芳香性和额外的稳定性。特别地，具有六个相连B环的完美体心立方AcB(6')和AcB可以在一维、二维和三维上扩展，形成一维的AcB(11')、二维的AcB(12')和三维的AcB(13')纳米材料，呈现出一种从金属硼化物纳米团簇到其低维纳米材料的基于硼的自下而上的方法。
