Synthesis And Properties Of Near-Infrared-Emitting Cyclometalated Platinum Complexes And Small Molecules Photo-voltaic Materials Based On Arylamine Units

The research progress about NIR organic electroluminescent materials(OELMs)and small molecules organic photovoltaic materials(SMOPMs),as well as their devices were reviewed in this dissertation.The synthesis and properties of cyclometalated platinum complexes for near-infrared organic-light-emitting diode(NIR-OLED)and small molecules for organic solar cells(SM-OSCs)are carried out in order to solve the current problems,such as few types and low efficiency for the NIR-OELMs and low power conversion efficiency for the SMOPMs.The main contents for this dissertation are as follows:1.Three kinds of platinum complexes with donor–acceptor(D-A)frameworks,i.e.(TPA-BTPy)Pt(pic),(TPA-BTPy-Fl)Pt(pic)and [Fl(TPA-BTPy)2]Pt2(pic)2 are respectively designed and synthesized.Compared to mono-nuclear platinum complexes and their free ligands,this dinuclear one of [Fl(TPA-BTPy)2]Pt2(pic)2 shows an obvious interaction from the platinum atom to ligand.The single-emissive-layer polymer light-emitting devices doped with [Fl(TPA-BTPy)2]-Pt2(pic)2 display a strong electroluminescence with dual emission peaks at 780 and 600 nm at a dopant concentration over 4 wt%.A maximum external quantum efficiency of 0.02% with a radiance of 59 ?W cm-2 is obtained.2.Two D-A-type salophen tetradentate platinum(II)compleses Pt-sal-2TPA and Pt-sal-2TPABT were obtained by introducing the substituted group TPA and TPABT in the 3,6-position of their parent complex Pt-sal.Using Pt-sal-2TPA and Pt-sal-2TPABT as a single dopant,the polymer light-emitting devices(PLEDs)exhibited deep red and near-infrared emissions,respectively.The EL peaks at 644 nm with external quantum efficiency(EQE)of 2.44% and 703 nm with an EQE of 0.88% were observed in the Pt-sal-2TPA and Pt-sal-2TPABT doped devices,respectively.3.By changing the substituted positions of dual TPAPZ units,two novel tetradentate platinum(II)salophen complexes w-Pt-sal-2TPAPZ and h-Pt-sal-2TPAPZ were synthesized and characterized.The platinum(II)salophen w-Pt-sal-2TPAPZ and h-Pt-sal-2TPAPZ exhibited a deep red emission at 653 nm with maximum external quantum efficiency of 0.1% and a near-infrared emission at 695 nm with maximum external quantum efficiency of 1.36% in the single-emissive-layer polymer light-emitting devices,respectively.4.Two novel tetradentate bis-cyclometalated platinum(IV)complexes of TPA-2q-Pt Cl2 and 3TPA-2q-Pt Cl2 with C^N*N^C cyclometalated ligands and two coordinatedchlorine atoms were synthesized and characterized.Using one of platinum(IV)complexes of TPA-2q-Pt Cl2 and 3TPA-2q-Pt Cl2 as a single dopant,the single-emissive-layer PLEDs exhibited an outstanding NIR EL emission.The EL peaks at 733 nm with an EQE of 0.87%,radiant intensities of 144 ?W/cm-2 and 750 nm with an EQE of 0.85%,radiant intensities of 164 ?W/cm-2 are observed in the TPA-2q-Pt Cl2 and 3TPA-2q-Pt Cl2 doped devices,respectively.5.Two novel D-A-Ar-type small molecules of TPA-DPP-PN and TPA(DPP-PN)2 were synthesized and characterized.Significantly improved photovoltaic performances were observed for both small molecules containing the planar PN terminal in comparison with those for their parent D-A-type molecule of TPA-DPP.The highest power conversion efficiency(PCE)of 3.42% was obtained in the solution-processed TPA(DPP-PN)2-based solar cells using [6,6]-phenyl-C-71-butyric acid methyl ester(PC71BM)as acceptor.The PCE value is 8.76 times higher than those of the TPA-DPP-based solar cells.6.Two novel linear-shape small molecules of Cz(DPP-PN)2 and Fl(DPP-PN)2 were synthesized and characterized.The Cz(DPP-PN)2 and Fl(DPP-PN)2 molecules with planar centers exhibited better photovoltaic performance than the TPA(DPP-PN)2 with a non-planar center in the solution-processed organic solar cells using [6,6]-phenyl-C61-butyric acid methyl ester(PC61BM)as acceptor.The highest power conversion efficiency of 4.13% was obtained in the Fl(DPP-PN)2 based cell.7.A novel triangular-spiral conjugation molecule of TPA(DPP-PN)3 and its counterpart of TPA-3DPP without the PN terminal were prepared.A hole mobility of 1.67×10-4 cm2 V-1 s-1 was obtained for the TPA(DPP-PN)3/PC71 BM blended film,which is 2.1 times higher than that of the TPA-3DPP/PC71 BM blended film.Furthermore,the TPA(DPP-PN)3/PC71BM-based organic solar cells presented better photovoltaic property with a maximum power conversion efficiency of 3.67%,which is 1.9 times higher than that of TPA-3DPP/PC71BM-based devices.