共轭平面富硼团簇及H/Au/BO/BS等瓣相似性研究

Boron hydrides and boron oxides are important boron compounds. Extensive investigations have been performed on the hydrogen-rich and oxygen-rich clustetrs, while little is known about boron-rich binary clusters, their structural transitions, and the relationship between boron-rich clusters and their corresponding hydrocarbon counterparts. We will perform in this project a combined first-principles calculation and photoelectron spectroscopy investigation on the global minima and 2D-3D structural transitions of boron-rich B-H, B-O, B-S, and B-Au binary clusters, including building the relationship between conjugated double-chain polyboroenes, polyboroynes, and monocyclic boron-rich binary clusters with conjugated single-chain polyenes, polyynes, and monocyclic hydrocarbons, expanding the H/Au/BO/BS isolobal analogy to a wider range of boron-rich compounds, establishing the concept of π plus σ double conjugation in boron chemistry, and exploring the possibility of monocyclic boron oxide clusters as a new class of effective inorganic ligands, aiming to facilitate future researches on boron-rich nano-sheets, nano-cages, and nano-ribbons.

硼-氢及硼-氧团簇是重要的含硼化合物，目前对富氢和富氧团簇研究比较充分，对富硼团簇及其结构过渡则知之甚少，对富硼硼氢及硼氧团簇与相应碳氢化物之间的对应关系也尚不清楚。本申请课题将采用第一性原理计算和光电子能谱实验相结合的方法，系统研究富硼硼氢、硼氧、硼硫及硼金团簇的全局极小及其2D-3D结构过渡，建立共轭双链硼烯、硼炔及环状富硼二元团簇与共轭单链烯烃、炔烃及稠环芳香烃结构对应关系，拓宽H/Au/BO/BS等瓣相似性, 确立硼化学中的π-与σ-双共轭概念，并探讨环硼氧团簇作为新颖过渡金属配体的可能性，为进一步研究富硼平面、笼状和带状纳米结构奠定基础。

本项目通过理论计算并结合光电子能谱实验，主要研究了硼羰基化学、H/Au/BO/BS等瓣相似性、共轭双链硼烯、裸硼团簇及其金属掺杂体系。发现了系列双链的硼羰基化合物，该双链结构具有和双重芳香性，拓展了硼羰基化学和有机碳氢化物的类似性。首次在实验上证明具有菱形B2O2单元的B3O3、B3O3H和B4O40/中存在4c-4e o键等。首次发现由硼双链交织而成的硼球烯团簇B40-/0及B39-，并建立了硼球烯家族Bnq (n=36-42, q=n-40)。研究发现，这些笼状硼球烯均由双链交织而成，符合和双离域成键。理论与实验结合发现了不同尺寸的含六元孔洞的准平面裸硼团簇，以双胞胎孔洞的B35-结构为例，其双孔结构预示了硼墨烯材料的结构特征。理论预测杂硼球烯和杂硼墨烯，提出硼球烯的前躯体H-硼墨烯及其金属掺杂结构。发现配位数最高的双环管状分子Ta@B20-。本项目在硼化学多个方面有原创性贡献，硼球烯的发现则开创了与富勒烯化学平行的硼球烯化学新领域。