Synthesis, Aggregation And Photochemical Probe Properties Of Perylene Diimide Derivatives

Perylene diimides?PDIs?and perylene derivative are red pigment and vat dyes with exceptional chemical,thermal,weather stability as well as their excellent optical and electronic properties.They have been applied to pigments such as laser dyes,photovoltaic devices,automotive finishes,fluorescent light collectors,and materials for single molecule spectroscopy.PDIs could be also good materials for fluorescent probes and they show strong fluorescence with wide visible ranges and high photostability.However,owing to aggregation of perylene chromophores,PDIs display poor solubility and very weak fluorescence which limits their applications,especially in biological field.The modification on structure of PDIs is usually achieved by introducing side groups at the imide position or to the bay position.Substitution at the imide position can improve the solubility of PDIs in solvent,affecting the packing behavior of PDIs in the solid state,without changing their photophysical properties significantly.While substitution at the bay position can increase solubility of PDIs in solvent but will change their photophysical properties.The perylene tetra-?alkoxycarbonyl??PTBAC?with four carboxylic ester groups attached decreased their?-?stacking,show excellent fluorescence and is more soluble in organic solvents.Incorporating heteroatom into the perylene plan can change the photochemical properties and electronic structures of PDIs.Furthermore,a variety of intermolecular interactions would be also induced by the highly?-extended heteroarene,such as heteroatom-heteroatom interactions and van der Waals interactions.Also it is highly desirable to obtain water soluble PDIs for their broader applications.Based on the current investigation of PDIs,this thesis report the self-assembly of three perylene diimide dyes bearing unsymmetrical substituents at bay position,designs two novel fluorescence probes to fluoride anion and synthesis a amino acid functionalized water-soluble perylene diimide.The main contents are as follows:1.Self-assembly,optical and electrical properties of perylene diimide dyes bearing unsymmetrical substituents at bay positionPerylene diimides?PDIs?are a kind of the most developed organic fluorescent materials due to their chemical,thermal,weather stability as well as optoelectronic properties,high luminescence efficiency,and can be used to form well-tailored supramolecular structures.But heavy aggregation caused quenching?ACQ?effect in solid state has smartly limited their applications.We have easily solved this problem by chemical modification of the PDI core with only phenoxy moietie at one of the bay position.In this paper,we report two perylene bisimides with small rigid substituents,1-phenol-N,N?-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide?PDI 1?and 1-p-chlorophenol-N,N?-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide?PDI 2?possess both well defined organic nanostructures and high fluorescence quantum yield in the solid state.In contrast,1-propanol-N,N?-dicyclohexyl perylene-3,4,9,10-tetracarboxylic diimide?PDI 3?bearing a straight chain only shown weak orange fluorescence.Morphological inspection showed that PDI 3 easily form well-organized microstructures despite the junction of the PDI core with a straight chain.The present strategy could provide a generic route towards novel and advanced fluorescent materials and these materials may find various applications in high-tech fields.2.Novel fluorescent probes for fluoride anion based on hydroxy-substituted perylene tetra-?alkoxycarbonyl?derivativesThe fluoride anion?F^-?sensing abilities of 1-hydroxyl-tetra?n-butoxyloxycarbonyl?perylene?probe 1?and 1-hydroxyl-mono-five-membered S-heterocyclic annulated tetra?n-butoxyloxycarbonyl?perylene?probe 2?were studied through visual detection experiment,UV-Vis,fluorescence,and ¹H NMR titrations.The probes were sensitive and selective for distinguishing F^-from other anions(Cl^-,Br^-,I^-,SO₄^-,PF₆^-,H₂PO₄^-,BF₄^-,ClO₄^-,OH^-,CH₃COO^-,and HPO₄^2-)through a change of UV–Vis and fluorescence spectra.The absorption and fluorescence emission properties of the probes 1 and 2 arise from the intermolecular proton transfer?IPT?process between H⁺on the phenolic O position and the F^-anion.The sensing mechanism was supported by theoretical investigation.Moreover,probe-based test strips can detect F^-without other additional equipment,and they can be used as fluorescent probes for monitoring F^-in the living cells.3.Study on the interaction between bovine serum albumin and a water soluble perylene derivativeN,N'-bi?L-glutamic amine?-perylene-3,4;9,10-dicarboxylic diimide?PTCDG?was synthesized and characterized,which was water soluble and yielded high fluorescent quantum.The interaction between PTCDG and biomolecule Bovine Serum Albumin?BSA?was investigated with fluorescence and absorbance spectroscopy techniques,as well as the influence of the ion intensity on the interaction.The results revealed that teeny BSA could decrease the fluorescence intensity of PTCDG,and the quenching efficiency was altered with change of BSA surface charge.Meanwhile,the fluorescence intensity of PTCDG increased and the fluorescence of BSA was quenched by PTCDG.The spectra showed an isoacitinic emission point at 515 nm,demonstrating the existence of the interaction or energy transfer between PTCDG and BSA.