Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.

Synthesis, Spectroscopic Properties, and Stabilities of Ternary Europium Complex in SBA-15 and Periodic Mesoporous Organosilica: A Comparative Study

Ternary europium complex Eu(tta)(3)phen was covalently bonded with the general mesoporous. material SBA-15 and SBA-15-type of periodic mesoporous organosilica (PMO) material via impregnation of Eu(tta)(3)center dot 2H(2)O into phen-S15 and phen-PMO, respectively, through a ligand exchange reaction. The parent materials of phen-S15 and phen-PMO were synthesized by co-condensation of tetraethylorthosilicate (TEOS) or 1,2-bis(triethoxysilyl)ethane (BTESE) and the functionalized chelate ligand 5-(N,N-bis(3-triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as template, which were confirmed by SEM, XRD, FTIR, Si-29 CP-MAS NMR, and N-2 adsorption measurements.

Near-infrared luminescent mesoporous MCM-41 materials covalently bonded with ternary thulium complexes

Two beta-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)(3)phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)(3)phen-MCM-41 (L = tta, tfnb)]. The Tm(L)(3)phen-MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle Xray diffraction (XRD) and N-2 adsorption/desorption, and they show characteristic mesoporous structure of MCM-41.

Near-infrared luminescent xerogel materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III)] complexes

A beta-diketone ligand 4,4,5,5,5-pentafluoro-1-(2-naphthyl)-1,3-butanedione (Hpfnp), which contains a pentafluoroalkyl chain, was synthesized as the main sensitizer for synthesizing new near-infrared (NIR) luminescent Ln(pfnp)(3)phen (phen = 1,10-phenanthroline) (Ln = Er, Nd, Yb, Sm) complexes. At the same time, a series of lanthanide complexes covalently bonded to xerogels by the ligand 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) were synthesized in situ via a sol-gel process. [The obtained materials are denoted as xerogel-bonded Ln complexes (Ln = Er, Nd, Yb, Sm).] The single crystal structures of the Ln(pfnp) 3phen complexes were determined.

Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

The crystal structure of a ternary Tm(DBM)(3)phen complex (DBM - dibenzoylmethane; phen = 1. 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM)(3)phen C59H47N2O7Tm, monoclinic P21/c, a = 19.3216(12) A, b = 10.6691(7) A, c = 23.0165(15)A, alpha = 90, beta = 91.6330(10), gamma = 90, V = 4742.8(5) A(3), Z = 4. The properties of the Tm(DBM)(3)phen complex and the corresponding hybrid mesoporous material [Tm(DBM)(3)phen-MCM-41] have been studied. The results reveal that the Tm(DBM)(3)phen complex is successfully covalently bonded to MCM-41.

Five supramolecular compounds of water-soluble sulfonylcalix[4]arenetetrasulfonate showing two calixarene conformations

Five new compounds of sulfonylcalix[4]arenetetrasulfonate (SC4AS), [H7Na(H2O)(3)(SC4AS)(phen)(5)](H2O)(11.9) (1), [H6Mn(H2O)(4)(SC4AS)(phen)(5)] (H2O)(12.7) (2), [Cu-4(SC4AS) (phen)(6)] (H2O)(4.5) (3), {[Cu (2)(SC4AS) (bpy)(2)][Cu(bpy)(2)(H2O)](2)} (H2O)(6.6) (4), and {[Zn-2(SC4AS) (phen)(2)][Zn(phen)(2)(H2O)(2)](2)} (H2O)(7) (5) (where phen 1,10-phenanthroline and bpy = 2,2'-bipyridine), were synthesized by a hydrothermal method and structurally determined by single crystal X-ray diffraction. The SC4AS ligand adopts partial cone conformation in compounds 1 and 2 and 1,2-alternate form in compounds 3-5. According to the structural analysis and density functional theory (DFT) calculations, we suggest that the metal can affect the conformation of SC4AS.

Assembly of Seven Supramolecular Compounds with p-Sulfonatocalix[6]arene

Seven supramolecular compounds comprising p-sulfonatocalix[6]arene and transition metals, {[Cu(Imz)-(phen)(H2O)](4)[C6AS]}center dot 10H(2)O (1), {[Cu(Imz)(2)(phen)](2)[Cu(Imz)(phen)(H2O)(2)](2)[C6AS]}center dot 13.3H(2)O (2), {[M(phen)(2)(H2O)]-[(M(phen)(2)](2)[C6AS]}center dot nH(2)O (3 and 4) (3: M = Co and n = 29.6; 4: M = Zn and n = 29.9), {[Cu(phen)(2)](4)[C6AS]}(2)center dot 13H(2)O (5), [H3O](2)[Co(phen)(3)](2)[C6AS]center dot 10.7H(2)O(6), and [Cu(phen)(2)(H2O)](2){[Cu(phen)(2)](2)[C6AS]}center dot 8H(2)O(7)(phen = 1,10-phenanthroline, C6AS = p-sulfonatocalix[6]arene, Imz = imidazole), have been synthesized by a hydrothermal method and structurally characterized by IR spectroscopy, thermogravimetric-differential thermal analysis (TG-DTA), and single crystal X-ray diffraction.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Efficient organic electroluminescent devices based on an organosamarium complex

Several organic electroluminescent devices with different device structures were fabricated based on an organosamarium complex Sm(HFNH)(3)phen[HFNH=4, 4, 5, 5, 6, 6, 6-heptafluoro-l-(2-naphthvl)hexane-1, 3-dione; phen=1, 10-phenanthroline] as emitter. Their electroluminescent properties were investigated in detail. Although the devices with the optimal structure ITO/TPD (50nm)/ Sm(HFNH)(3)phen (xwt%):CBP (50nm)/BCP (20nm)/AIQ (30nm)/LiF (1 nm),/Al (200nm) show high brightness (more than 400cd/m(2)) and high current efficiency (about 1 cd/A), there are emissions from CBP, BCP and even from AIQ existing in the electroluminescence (EL) spectra besides emission from Sm(HFNH)(3)Phen. The reason to this was discussed. The device with the structure ITO/TPD (50 nm)/ Sm(HFNH)(3)phen (50 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 118 cd/m(2) and current efficiency of 0.029 cd/A, and shows emissions from AIQ and Sm(HFNH)(3)phen at high voltages. However, with the BCP hole-block layer added, the device [ITO/TPD (50 nm)/Sm(HFNH)(3)phen (50 nm)/BCP (20 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm)] exhibits pure Sm3+ emission in 2 the EL spectra even at high voltages, with the maximum current efficiency of 0.29cd/A and brightness of 82cd/m(2)

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.

Improved efficiency by doping blue iridium (III) complex in europium complex-based light-emitting diodes

We demonstrated high-efficiency red organic light-emitting diodes (OLEDs) employing a europium complex, Eu (III) tris( thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen)), as an emitter and a blue electrophosphorescent complex, Iridium ( III) bis[4,6-di-fluorophenyl-pyridinato-N,C-2] picolinate (FIrpic), as an assistant dopant codoped into 4,4-N, N-dicarbazole-biphenyl (CBP) host as an emissive layer. A pure red electroluminescence (EL) only from Eu3+ ions at 612 nm with a full width at half maximum of 3 nm was observed and the EL efficiency was significantly enhanced. The maximum EL efficiency reached 7.9 cd A(-1) at 0.01 mA cm(-2) current density, which is enhanced by 2.8 times compared with electrophosphorescence-undoped devices. The large improvements are attributed to energy transfer assistance effects of FIrpic, indicating a promising method for obtaining efficient red OLEDs based on rare-earth complexes.

Triboluminescence of a new europate complex

A new europium (III) complex Eu(HFNH)(3)Phen (HFNH: 4, 4, 5, 5, 6, 6, 6-heptafluoro-1-(2-naphthyl) hexane-1,3-dione; phen: 1, 10-phenanthroline) was synthesized and its triboltuninescent phenomenon was observed. Photoluminescence and triboluminescence spectra were successfully determined. The most intense triboluminescent emission originates front the transition of the, central Eu3+ ion from D-5(0) level to F-7(2) level. The triboluminescent spectrum is basically similar to that of photoluminescence, which correlates with the disorders of F atoms.

Covalent linking of near-infrared luminescent ternary lanthanide (Er3+, Nd3+, Yb3+) complexes on functionalized mesoporous MCM-41 and SBA-15

The near-infrared (NIR) luminescent lanthanide ions, such as Er(III), Nd(III), and Yb(III), have been paid much attention for the potential use in the optical communications or laser systems. For the first time, the NIR-luminescent Ln(dbm)(3)phen complexes have been covalently bonded to the ordered mesoporous materials MCM-41 and SBA-15 via a functionalized phen group phen-Si (phen-Si = 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline; dbm = dibenzoylmethanate; Ln = Er, Nd, Yb). The synthesis parameters X = 12 and Y = 6 h (X denotes Ln(dbM)(3)(H2O)(2)/phen-MCM-41 molar ratio or Ln(dbM)(3)(H2O)(2)/phenSBA-15 molar ratio and Y is the reaction time for the ligand exchange reaction; phen-MCM-41 and phenSBA-15 are phen-functionalized MCM-41 and SBA-15 mesoporous materials, respectively) were selected through a systematic and comparative study. The derivative materials, denoted as Ln(dbM)(3)phen-MCM-41 and Ln(dbm)(3)phen-SBA-15 (Ln = Er, Nd, Yb), were characterized by powder X-ray diffraction, nitrogen adsorption/desorption, Fourier transform infrared (FT-IR), elemental analysis, and fluorescence spectra. Upon excitation of the ligands absorption bands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions.

Highly efficient red electroluminescence from stacked organic light-emitting devices based on a europium complex

Stacked organic light-emitting devices (OLEDs) based on a europium complex Eu(TTA)(3) (Tmphen) (TTA = thenoyltrifluoroacetone,Tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were fabricated. In this stacked OLEDs, Li:BCP/V2O5 was used the intermediate charge generation layer sandwiched between two identical emissive units consisting of TPD/CBP:DCJTB:Eu(TTA)(3)(Tmphen)/BCP. As expected, the brightness and electroluminescent (EL) current efficiency were approximately enhanced by double times that of conventional single-unit devices. The stacked OLEDs showed the maximum luminance up to 3000 cd/m(2) at a current density of 190 mA/cm(2) and a current efficiency of 14.5 cd/A at a current density of 0.08 mA/cm(2). At the brightness of 100 cd/m(2), the current efficiency reached 10 cd/A at a current density of 1.6 mA/cm2.

Crystal structure of a luminescent complex Sm(HTH)(3)Phen

The crystal structure of Sm(HTH)(3)Phen [HTH: 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione, Phen: 1,10-Phenanthroline] has been determined by single crystal X-ray diffraction and the coordination geometry of Sm atom is a dodecahedron. The complex can give the characteristic luminescence of Sm3+ upon UV excitation.