General Information: All reactions were performed under nitrogen. Solvents were carefully dried and distilled from appropriate drying agents prior to use. Commercially available reagents were used without further purification unless otherwise stated. All reactions were monitored by thin-layer chromatography (TLC) with Merck pre-coated glass plates. Flash column chromatography and preparative TLC were carried out using silica gel from Merck (230-400 mesh). Fast atom bombardment (FAB) mass spectra were recorded on a Finnigan MAT SSQ710 system. Proton NMR spectra were Ferrocene was added as a calibrant after each set of measurements, and all potentials reported were quoted with reference to the ferrocene-ferrocenium (Fc/Fc + ) couple at a scan rate of 100 mV s −1 .Thermal analyses were performed with the Perkin-Elmer TGA6 thermal analyzer.
Dimerization of monoporphyrinate lanthanide complexes [Yb(Por)(H(2)O)(3)]Cl, (Por = TTP(2-), TMPP(2-) and TPP(2-)) in the presence of sterically hindered tripodal ligand, zinc Schiff-base, dilute HCl, K(2)CO(3) solution, 4,4'-bipyridine (bipy), and basic 8-hydroxyquinaldine (HQ) solution was observed in CH(2)Cl(2) at room temperature. Six neutral dimeric lanthanide porphyrinate complexes, [Yb(TTP)(mu-OH)](2)(mu-THF) (1), [Yb(TMPP)(mu-OH)(H(2)O)](2) (2), [Yb(TPP)(mu-OH)(mu-H(2)O)](2) (4), [Yb(TMPP)(mu-Cl)(H(2)O)](2) (5), [Yb(TMPP)(mu-OH)](2)(THF) (6) and [Yb(TPP)](2)(mu-OH)(mu-Q) (7), were obtained. X-Ray diffraction studies showed that for the dimers, the two lanthanide ions were bridged by OH(-), Cl(-) or H(2)O. Photoluminescent studies showed that the porphyrinate dianion acted as an antenna, transferred its absorbed visible energy to the lanthanide ion and enabled the latter emitting in the near-infrared (NIR) region. In general, the NIR emission is more intense for the dimers than for the monomers, and the NIR emission intensity decreases as the number of O-H oscillators present in the molecule increases.
Synthetic routes to novel oligomeric and polymeric platinum(II)-containing alkynylsilanes were developed. Soluble and thermally stable platinum(II) poly(alkynylsilanes) trans-[−Pt(PBu3)2C⋮C(p-C6H4)C⋮CSiPh2C⋮C(p-C6H4)C⋮C−] n were prepared in good yield by CuI-catalyzed condensation polymerization of trans-[PtCl2(PBu3)2] with HC⋮C(p-C6H4)C⋮CSiPh2C⋮C(p-C6H4)C⋮CH. The regiochemical structure of the polymer was studied by NMR (1H, 13C, 29Si, and 31P) spectroscopy. We report the optical absorption and photoluminescence spectra of such metal-based organosilicon polymer and compare the data with their oligomeric model complexes trans-[Pt(Ph)(PEt3)2C⋮C(p-C6H4)C⋮CSiPh2C⋮C(p-C6H4)C⋮CPt(Ph)(PEt3)2] and trans-[Pt(Ph)(PEt3)2C⋮C(p-C6H4)C⋮CSiPh2C⋮C(p-C6H4)C⋮CPt(PBu3)2C⋮C(p-C6H4)C⋮CSiPh2C⋮C(p-C6H4)C⋮CPt(Ph)(PEt3)2]. Our studies indicate that such organometallic poly(alkynylsilanes) show a strong triplet emission with a very high efficiency of intersystem crossing from the S1 singlet excited state to the T1 triplet excited state. The dependence of intersystem crossing and the spatial extent of singlet and triplet excitons as a function of the central spacer group is discussed in polymetallaynes possessing SiPh2, C6H4 and Pt(PR3)2 (R = Et, Bu) linkers. The photoconducting properties of such silicon-linked platinum polyyne are described.
In linear optics, the metasurface represents an ideal platform for encoding optical information because of its unprecedented abilities of manipulating the intensity, polarization, and phase of light wave with subwavelength meta-atoms. However, controlling various degrees of freedom of light in nonlinear optics remains elusive. Here, we propose a nonlinear plasmonic metasurface working in the near-infrared regime that can simultaneously encode optical images in the real and Fourier spaces. This is achieved by designing a diatomic meta-molecule, which enables the independent control of the nonlinear geometric phase, polarization, and intensity of second harmonic waves. The proposed nonlinear diatomic metasurface provides an ultracompact platform for implementing multidimensional optical information encoding and may hold great potential in optical information security and optical anticounterfeiting.
We demonstrate a highly efficient white organic light emitting device with fluorescent small molecule 4,4′-bis(9-(1-naphthyl)anthracene-10-yl)biphenyl (BUBH-3). With a simple device architecture of indium tin oxide/tris 4,4′,4″-tris-N-naphthyl-N-phenylamino-triphenylamine (60nm)∕N,N′-bis-(1–naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (10nm)/BUBH-3 (45nm)∕Alq3 (15nm)∕LiF (1nm)∕Al (150nm), a white light with CIEx,y color of (0.31,0.36) was generated. The device achieved one of the best single-emitting-material electroluminescence performance of white organic light-emitting devices with efficiencies of 7.0cd∕A and 3.17lm∕W at 6.9V.
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