含多个氮杂环卡宾（NHC）基团的新型大环化合物与非金属战略元素（硼，硅，磷）加合物的研究

The compounds containing strategic nonmetallic element(s) boron (B), silicon (Si), and/or phosphorus (P) play important roles in many disciplinary fields (e.g., chemistry). A series of Noble Prize winners got success because of their contribution on the research of these compounds. Herein, the proposal try to combine the study of two frontiers: (1) the adducts between N-heterocyclic (NHC) and strategic nonmetallic element boron (B), silicon (Si),and/or phosphorus (P) (i.e., NHC-X (X = B, Si, P)); (2) the study of supramolcular macrocyclic host chemistry. It is proposed to design and synthesis a series of new macrocyclic compounds containing multi-N-heterocyclic (NHC) groups with fine-tuned electronic property and reactivity. Furthermore, different bridged groups are picked out to control the cavities of macrocyclic hosts, also the locations, orientations and reactivities of their NHC sites. Base on the special cavities, unique chemical environments, and pre-organized NHC reacting sites, novel macrocycles will be used to effectively construct the adducts between NHC and strategic nonmetallic element(s) boron (B), silicon (Si),and/or phosphorus (P) (i.e., NHC-X (X = B, Si, P)). Clear characterization, precise control, and physicochemical property of NHC-X (X = B, Si, P) are also included into this study to realize further transfer of element(s) boron (B), silicon (Si),and/or phosphorus (P) in organic functional molecules and supramolecular self-assembly systems. To our knowledge, the similar study has not been reported before, and will provide new strategies to obtain new bonding modes, novel reaction styles, and unexpected functional molecules containing these strategic nonmetallic element(s), including boron (B), silicon (Si),and/or phosphorus (P) .

非金属战略元素硼（B）、硅（Si）、磷（P）相关化合物的研究在化学等多个学科领域中举足轻重，多项诺贝尔奖项均与上述化合物的研究相关。本项目拟将方兴未艾的氮杂环卡宾（NHC）形成NHC-X（X = B, Si, P）加合物的研究与超分子大环化合物的前沿研究领域相结合，以设计合成一系列新型大环化合物为起点，通过调控其具有的多个NHC单元的电子性质和反应活性，同时利用桥连基团的选择控制大环空腔结构及NHC反应位点性质、空间分布和取向。综合大环化合物的特定空腔结构、独特化学环境和预组织的NHC反应位点，对大环化合物稳定的新型多元NHC-X（X = B, Si, P）加合物进行高效合成、明晰表征、精确调控及理化性能研究，以期实现后继的B，Si和P元素在有机功能分子及自组装体系中的迁移和转化。该类研究目前未见文献报道，可提供新的思路和途径，发现并探讨这些元素涉及的新成键模式、新反应类型和新型功能分子。

非金属战略元素硼（B）、硅（Si）、磷（P）相关化合物的研究在化学等多个学科领域中举足轻重，多项诺贝尔奖项均与上述化合物的研究相关。本项目将方兴未艾的氮杂环卡宾（NHC）形成NHC-X（X = B, Si, P）加合物的研究与超分子大环化合物的前沿研究领域相结合，设计合成一系列具有多个NHC前体单元的新型大环化合物，探讨其生成的NHC的反应活性，获得了具有高反应活性的该类大环化合物的酸式碳酸盐,并通过单晶衍射进行了表征；对该类大环和贵金属物种的复合进行了系列研究，以应用于后继的大环化合物稳定的新型多元NHC-X（X = B, Si, P）加合物的制备；同时成功制备了系列含多个NHCH+基团的新型大环化合物与含B元素的活性物种（如BH3, 9-BBN, BF3）的稳定加合物并进行了初步表征，研究表明该类分子具有特殊的荧光特性，可用于新型光学材料的开发。本项目研究为以具有多个NHC前体基元的大环分子为配体，与非金属战略元素(B, P 或Si)加合进而获得新成键模式、新反应类型和新型功能分子奠定了基础。