Study Of Synthesis And Properties Of Osmapentalenes/Osmapentalynes

Organometallic chemistry is a discipline that studies synthesis,structure,reactivity,performance and application of compounds containing metal-carbon bond.Metallaaromatics with both the characteristics of classic aromatic and organometallic compounds,have received extensive attention.In recent years,the original"Carbolong Chemistry" of our group has been developing continuously,a series of carbolong complexes with novel structure were constructed,which show amazing application potential in photoacoustic imaging,photothermal therapy,single molecule conductance,solar energy conversion and perovskite solar cells.This dissertation takes the construction of new types of osmapentalenes/osmapentalynes as the main line of exploration and studies the reactivities of phenanthrometallapentalyne,the firstα-azametallapentalene,and metallacyclopropene with σ-aromaticy.A series of novel carbolong complexes were obtained,which enrich the types of metallaaromatics.In addition,based on the above-mentioned reactivity studies,a series of osmapentalynes/osmapentalenes containing diphenylphosphine oxide(DPPO)were synthesized by further structural modification.This dissertation consists of the following six chapters:In Chapter 1,according to the research of this dissertation,a brief review of transition-metal-containing metallaaromatics and cyclic metallavinylidenes is given.The“carbolong chemistry”developed by our group is also briefly reviewed.The main idea and purpose of this dissertation were proposed.In Chapter 2,a biphenyl-type carbolong was designed and synthesized,and phenanthroosmapentalyne and osmapentalenone containing the smallest metallavinylidene angle were constructed under different reaction condition,the reactivity of both were also investigated.Studies show that the addition reaction of phenanthroosmallapentalyne with phenolic nucleophiles constructs a fused ring with lager conjugate system;phenanthroosmapentalyne undergoes addition reaction with sulfur and electrophilic substitution with halogen.Osmapentalenone 3-3 containing cyclic metallavinylidene would undergo carbonyl addition in the presence of electrophilic acid or methyl trifluoromethanesulfonate,and convert into corresponding phenoanthroosmapentalyne derivatives.In Chapter 3,the reactivity of the first α-azaosmapentalene were investigated,and a series of novel azaosmaaromatics were constructed.The reaction ofα-azametallapentalene with electrophiles destroyed the original azametallapentalene structure to form osmapyrroles.In the reaction of azametallapentalene with nucleophiles,the reaction positions are mainly in the azametallaaromatics ring and the metal center,and a novel fused-ring with a rare cyclic metallavinylidene was obtained.The aromaticity of a series of azaosmapentalene derivatives were also studied by density theoretical calculation(DFT).In Chapter 4,in the case of metallacyclopropene without ring-opening,the reactivity of eight-carbolong complex(osmapentalene fused with osmacyclopropene)were investigated,a series of new multidentate complex framework were realized without the additional substrates.Studies show that eight-carbolong complex can be converted into a series of carbolong complex with PCCCC-type pincer ligands in the presence of Lewis acid/oxidants.And under the combined action of imine derivatives 4-7 and silver salt,carbolong complex with PCCCCP-type pincer ligand was constructed,of which the reaction process has also been explored.In Chapter 5,the modification of eight-carbolong complex was investigated.Reacting eight-carbolong complex with tert-butoxide,a DPPO group substituted eight-carbolong complex were synthesis.A series of 7-aryl vinyl seven-carbolong complexes were constructed by the reaction of eight-carbolong complex containing DPPO group with aryl aldehydes in the presence of CF3COOH.Preliminary exploration of the luminescence of these complexes were performed,which are expected to be used in biomedical applications.In Chapter 6,the innovation of the dissertation is concluded and the prospect of this research is presented.