Synthesis And Properties Of Conjugated Derivatives Of Trinaphtho[3.3.3]propellane

In recent years,3D organic conjugated materials have attracted wide attention in supramolecular assembly and organic semiconductors due to their beautiful topological structures,unique electron-rich cavity and crystal packaging modes,and their ability to realize multidirectional carrier transport.However,compared with the more studied one-dimensional and two-dimensional materials,three-dimensional organic conjugated materials have fewer three-dimensional structural units,and most of them have poor solubility,which makes synthesis and separation relatively difficult.trinaphtho[3.3.3]propellane（TNP）is a typical three-dimensional structural unit with a large three-dimensional rigidπ-conjugate plane and electron cavity.Since the activity ofβcarbon of trinaphtho[3.3.3]propellane is much lower than that ofαcarbon,the current conjugate expansion is based on activatedαsites.Functionalization of less reaction positions is a challenging task.In this paper,Iridium catalyst and ligand were used for the first time to activate the C-H bond at theβ-site of trinaphtho[3.3.3]propellane.The borylation of TNP gave 6Bpin-TNP in a high yield of 85%,which is an important precursor of coupling and functional group conversion.This work provides new directions and material basis for conjugated extension of trinaphtho[3.3.3]propellane.In addition,based on the borylation precursor 6Bpin-TNP,a 3D curved polycyclic aromatic hydrocarbon with high strain structure was synthesized,and its semiconductor device performances was initially tested.the main research contents are as follows:1.In this work,the combination of[Ir（OMe）（COD）]₂（10mol%）and dtbpy（20mol%）was used as catalyst system,and B₂pin₂（12eq）was used as the boron source.Under mild reaction conditions,activation of C-H bonds at allβsites and borylation were completed in one step,and 6Bpin-TNP as coupled precursor was obtained.After the functional group conversion of 6Bpin-TNP,intermediate product coupled with borylation monomer by Suzuki crossing coupling reaction to obtain aromatization precursor with moderate yields.Obtained compound 3-14 by Scholl reaction is curved polycyclic aromatic hydrocarbon containing seven-membered rings based on trinaphtho[3.3.3]propellane.Device testing show that compound 3-14 emits blue light in organic light-emitting diodes,and the maximum luminance of the devices doped with different main materials can reach 4774cd/m².2.6Bpin-TNP was coupled with different aryl halides to obtain a series ofβ-site conjugate derivatives by Suzuki crossing coupling reaction.The bromo-benzene conjugated products yield the highest,up to 60%.Using two key steps of intramolecular dibromo homocoupling and reduction aromatization,cycloparaphenylene structure based on one-dimensional naphthalene ring model was synthesized.