Synthesis Of Fullerene Fragments And For Thei Organic Semiconductor Applications

Bowl-shaped PAHs,also known as buckybowls,can be regarded as fragments of fullerenes,and their"bowl-shaped"surface structure is due to the introduction of five-membered rings into the SP² hybrid six-membered ring network.Buckybowls have unique properties compared to planar PAHs,such as chirality,dynamic flipping,and supramolecular self-assembly.Bucky bowls have good stability and solubility,so they can control and optimize the molecular packing mode,exhibit good carrier transport properties,and are widely used in organic field effect transistors.The solution-phase method is commonly used to prepare buckybowls,but it needs to overcome the large molecular surface tension.At present,there is no mature route to prepare such molecules.The main work of this thesis is the preparation of C₇₀ fragment molecules and the study of their structure and device properties,which can be divided into the following two aspects:1.Using 1,5-dichloroanthraquinone as the starting point to introduce a chlorine atom,through the simple steps of Grignard reagent addition,palladium-catalyzed intramolecular cyclization,etc.,a compound with s-triisopropylphenyl substitution was designed and synthesized.Twoπ-conjugated bucky bowls with different planes:TIPP-Tri and TIPP-Tetra.The single crystal data of the two bucky bowls show that the size of theπ-conjugated plane of the parent nucleus has little effect on the bowl depth and inversion barrier.increases,the electron affinity decreases,the ionization energy increases,and the band gap decreases.2.Introduce a chlorine atom from 1,5-dichloroanthraquinone,react with Grignard reagent of 3-bromo-2-naphthalene acetal and conduct methoxylation of hydroxyl-containing intermediate to overcome the molecular Solubility problems,the use of Grignard reagent addition,palladium-catalyzed intramolecular cyclization reaction to prepare benzoperylene skeleton with two different substituent buckybowl molecules:TIBS-Tetra and DIPOS-Tetra.The self-assembly behavior of buckybowl and C₇₀ shows that DIPOS-Tetra molecules with longer alkyl chains have stronger binding to C₇₀,which is expected to be applied in the field of organic co-crystals.Its optoelectronic and theoretical calculations show that the substituents have no effect on the lowest occupied molecular orbital（LUMO）of the buckybowl molecules.Both buckybowls have the properties of P type materials,and the hole transport efficiencies of TIBS-Tetra and DIPOS-Tetra in organic field effect transistors are 8.34×10^-3 and 2.00×10^-2 cm²V^-1s^-1,respectively.