A Theoretical Study On Organic Fluoreniod #-Shaped Gridspiroarenes

Organic semiconductor materials have been widely applicated in the fields of display,laser due to advantages of low cost and flexibility,while they still lag in carrier mobility,stability and luminous efficiency.In order to establish an effective strategy of organic semiconductors with high mobility and luminous efficiency,on the basis of bulky molecular structure with well stability,we propose a strategy of organic semiconductor gridization.Different from most of mono-nanogrids such as laddertype nanogrids,windmill-type gridarenes,rhomboidal monogridarenes,#-shaped gridarene is a kind of orthogonally rigid scaffold with eight arms extending in four directions.In this paper,we design three #-shaped gridspiroarenes,and use density functional theory to investigative molecular structures,ring strain energies,noncovalent interactions,frontier molecular orbitals,ionization potentials,electron affinities,normal mode,absorption spectrums and especially effects of structures on reorganization energies.The specific results are as follows: 1.SFX-based and SITF-based gridspiroarenes have several following gridization effect,such as HOMO-LUMO gaps decrease 0.63 eV which cause red shift of 47 nm in absorption spectrums,ionization energies decrease 0.4 eV,electron affinities increase 0.7 eV,hole reorganization energies are 0.127 and 0.067 eV which decrease 0.03 and 0.1 eV,respectively;2.SCPDT-based gridspiroarenes have the ?-? stack effects which increase rigidity,and are confirmed by weak interactions visualization analysis.Several stack gridization effects are found such as bridged connections in LUMO,ionization energy decreases 0.46 eV,hole reorganization energy is 0.14 eV which decreases 0.297 eV;3.Gridspirofluorenes have the following featrures,such as low strain energy of 1.57 kcal/mol which indicates a high yield,the HOMO and LUMO improve delocalizations and have degenerate characters,the lowest hole reorganization energy is 0.056 eV which decreases 0.127 e V,with cyano substituents,electron affinity is-1.87 eV which increases 1.36 eV,electron reorganization energy is 0.087 eV which decreases 0.004 eV.All these results show that by strategies of gridization,#-shaped gridspiroarenes have very low reorganization energies,which are beneficial to improve the mobility,and provide theoretical guidance for the experimental design and synthesis of high mobility hole and electron transport organic semiconductor materials.