Doping Sumanene With Phosphorus And/or Chalcogens: Synthesis,Chemical Reactivity And Optoelectronic Properties

The PAHs with large?-conjugated system are suitable for application in organic electrinics.It has been documented that the optoelectronic properties and the chemcial reactivities of PHAs can be finely tuned by imbedding main group elements.In this dissertation,doping sumanene with chalcogens and phosphorus have been synthesised.Among these heterasumanenes,the benzylic position of sumanene have been successfully replaced by the elements S,Se,Te,and P.The chapters of the thesis are listed as follow:In chapter1,research background.The chemical engineering of polycyclic aromatic molecules,ie extension of the?-conjugated frameworks and embeding heteroatoms into the conjugated backbone,have been introduced.With that in mind,after a short introduction,we mainly summarized and highlight recent advance in the polycyclic heteroaromatic molecules,heteracorannulene.and heterasumanene.At last,we put forward the proposal of this thesis,that is,doping sumanene with the S/Se/Te/P.Then its optical properties and chemical reactivity will be discussed.In chapter2,the tritellurasumanene and its derivatives:synthesis and its optoelectronic properties.Tellurium(Te)has a narrow bandgap energy.The optoelectronic properties and packing motifs can be finely tuned by Te atom.In this chapter,the tritellurasumanene has been synthesised by the strategy of ultrasound assisted.Its valence adducts with halogens was also obtained.The tritellurasumanene shown a planar conjugated framworks and forms Te···Te(3.83 A)interactions in solid state.The optoelectronic properties and chemical reactivity of tritellurasumanene are quite different from trithiasumanene(1)and triselenasumanene(2).In chapter3,the synthesis,properties and chemical reactivity of the trichalcogenasumanenes containing various chalcogen atoms.It is a proven fact that the optoelectronic properties and the chemcial reactivities of sumanene can be finely tuned by imbedding chalogen atoms.The trichalcogenasumanenes containing various chalcogen atoms have been successfully synthesized.The crystal of TCSs indacated that the molecular geometry varies from bowl-shaped to planar with the increase of chalcogen size(S/Se/Te).The optical properties of sulfur-rich(4-5),selenium-rich(6-7)and tellurium-rich(8-9)were analogous to trithiosumanene(1),triselenasumanene(2)and tritellurasumanene(3),respectively.In this chapter,we investigated the chemical reactions of 4-7 with Oxone,H₂O₂,and Br₂.The results indicated that their reactivities are dominated by the heaviest atoms in the molecular.In chapter4,the synthesis and optical properties of the doping sumanenes with chalcogens and phosphorus.The five-ring of chalcogenoles could be opened by the strong base n-Bu Li.Doping sumanenes chalcogens and phosphorus(26-28)with chalcogen and phosphorus was been successfully obtained in one pot reaction.The trichalcogenasumanene(1-3)were used as raw material and replaced one chalcogen atom with"P=S"unit.In this chapter,we investigated the optical properties and crystallographic of 26-28.Due to the introduction of"P=S"unit,the bowl depth of26-28 were planar,and the electron-withdrawing group"P=S"shrinks the HOMO-LUMO gap as compared to trichalcogenasumanene(1-3).In chapter5,doping sumanene with chalcogens and phosphorus:coordination and optical properties.According to the hard and soft acids and bases theory,the S atom and the soft base of tellurium may coordinate with some metal ions.In this chapter,the"P=S"units of 26-28 shown optical response and coordination with Ag⁺.For example,26 shows selective fluorescence response with Ag⁺and the LOD was0.21?M.Due to coordination with Ag⁺,the bond lengths of C-P and C-X(X=S,Se,Te)were shrinked and the bowl-depths of the complexs was increased to 0.66?,0.42?and 0.40?,respectively.In this chapter,we firstly reported the Ag-Te dative bond between Ag⁺and Te atom on tellurophene.In chapter6,the novel reactivity of the PHAs and trichalcogenasumanenes containing tellurophenes.In chapter 3,we found that the reactivities of the trichalcogenasumanenes containing various chalcogen atoms are dominated by the heaviest atoms in the molecular.In this chapter,the tellura-Baeyer-Villiger oxidation of the trichalcogenasumanenes and HBT containing tellurophene is reported.Between Te-C bond of tellurophene was inserted an oxygen atom by oxidizing the electro-rich compound 5,7 and 29 with m CPBA or Oxone.The one-step transformation of tellurophene into chiral tellurinate lactone mono-30,mono-31 and mono-32 were achieved by the tellura-BV oxidation.The proposal mechanism of this reaction is listed as follow:1)Te-oxide was obtained by oxidizing compounds 7,8,and 29;2)Te-oxide undergoes tellura-Baeyer-Villiger oxidation and then the tellurinate lactone was obtain.Owing to the strong secondary bonding interaction(SBIs)of the"Te=O"unit on tellurinate lactone,the asymmetric configurations form U-shaped in the solid-state.