硼基纳米团簇的新颖结构、电子特性和化学成键: 准平面硼团簇、全硼富勒烯、硼羰基团簇

硼是典型缺电子元素。硼基纳米团簇与低维硼纳米材料具有独特的结构、化学成键和材料性质。本申请立足硼化学研究前沿，选择突破硼基纳米团簇的三个热点方向：(1) 表征中等尺寸的准平面硼团簇，确定其从二维向三维的结构过渡，并基于准平面硼团簇探索新型硼单层纳米结构的可能性。(2) 基于申请人2014年最新研究发现，开拓全硼富勒烯家族，探讨其结构、电子计数和化学成键的一般规则；研究全硼富勒烯的掺杂和化学修饰；理论上研究全硼富勒烯 (特别是修饰的全硼富勒烯) 在储氢方面的特殊性质。(3) 继续推进硼氧化物团簇与硼羰基化学，包括金属-硼羰基复合物，并理性设计基于硼氧体系的超卤素和飙卤素。本项目拟采用气相红外光解离谱学、光电子能谱学实验与全局结构搜索、高精度量子化学电子结构计算密切结合的技术路线，并以新颖结构、独特化学成键为特色。申请人是近年来在相关研究方向的重要开拓者，在本研究领域有深厚学术积累。

Boron is well-known for its intrinsic electron-deficiency, which leads to unique physical chemistry for the boron-based nanoclusters. We propose herein to study the structures, electronic properties, and chemical bonding for three boron-based nano systems. System 1, flat boron: We aim to determine the size for 2D-to-3D structural transition for boron clusters, to characterize the structures for a variety of yet unknown flat boron clusters, and to explore the viabilities for extended atomic-layer thick boron sheets. System 2, all-boron fullerenes: We propose to expand the family of all-boron fullerenes with different sizes, charge-states, and shapes, and to uncover the principles that govern their structures, electron counting, and bonding. System 3, boronyl (BO) chemistry: We plan to characterize new boron oxide clusters and metal boronyl complexes and to rationally design relevant superhalogens and hyperhalogens, which feature extremely high electron affinities. The project will be conducted using the combination of gas-phase infrared photodissociation spectroscopy, anion photoelectron spectroscopy, global structural searches, and electronic structural calculations. The project is expected to result in original experimental and theoretical findings and will help enrich the physical chemistry of boron at the nanoscale.