A Novel Class Of Functional Molecules Based On Chemically Modified Perylene At The Bay-and Ortho-position

Perylene and its derivatives can be viewed as a fusion of five benzene rings,which has a typical molecular structure of rylenes.As promising organic functional material molecules,perylene derivatives have widespread applications in many areas,such as organic dyes,organic light-emitting diodes,organic field-effect transistors,fluorescence probes and organic solar cells.Perylenequinonoid dyes,the special molecular sketon of perylene derivatives,have attracted the interesting of chemist,medicinal scientists and biologists for many years due to their intrinsic photobiological activity and electronic structure.However,the most of perylenequinonoid derivatives exist in fungi or natural plants,only a limited number of perylenequinonoid have been synthesized by chemists.In this thesis,a perylenequinonoid derivative was effectively prepared by intermolecular oxidative dehydrogenation coupling.Then,we designed a reversible fluorescent probe based on the redox reactivity of the "bay-region" carbonyl groups.In addition,a class of novel fused pyridazine aromatics,namely 1,2-diazabenzo[ghi]perylene derivatives,has been synthesized by condensation of carbonyl group and hydrazine hydrate.Consequently,its molecular structure and electronic properties were studied.Finally,we synthesized 2,5,8,11-tetrabromo-6,7-dihydroxy-1,12-perylenequinonoid from 3,6-dibromo-2,7-dihydroxynaphthalene in one step via oxidant mediated intermolecular radical coupling.After reduction of "bay region"carbonyl groups and alkylation of hydroxyl groups,the perylenequinonoid derivatives were transformed to parent perylene structure.Thus,a series of "bay region"-position and ortho-position substituted perylene derivatives were obtained.This concise synthetic strategy avoids the directly functionalized modification of perylene,and provides a new approach for the synthesis of novel perylene derivatives.Three parts were shown belows:(1)We facilely synthesized 6,7-dihydroxy-1,12-perylenequinonoid by a well-developed method.The reversible redox reactivity of "bay region" carbonyl groups inspired us to design a perylenequinonoid-based reversible fluorescence probe,which can reversible detect H2S2/HClO redox pair in solution and living cells.(2)A new type of pyridazine fused aromatics,1,2-diazabenzo[ghi]perylenes,was successfully synthesized from 2,7-dihydroxynaphthalene by intermolecular oxidative coupling followed by condensation reaction.These new compounds were characterized by X-ray crystallographic analysis,optical spectroscopy and electrochemistry,assisted by DFT calculations.They show a twisted structure and unique P-/P-and M-/M-enantiomer pairs in the single crystals,while in solution they exhibit intramolecular charge transfer character and emit at longer wavelength with a larger Stokes shift compared with the all-carbon analog.(3)We synthesized 2,5,8,11-tetrabromo-6,7-dihydroxy-1,12-perylenequinonoid from 3,6-dibromo-2,7-dihydroxynaphthalene in one step via oxidant mediated intermolecular radical coupling.After reduction and alkylation of"bay region" carbonyl,a series of "bay region"-positions and ortho-positions substituted perylene derivatives could be obtained.