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.

A high-performance tandem white organic light-emitting diode combining highly effective white-units and their interconnection layer

By utilizing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline:Li/MoO3 as an effective charge generation layer (CGL), we extend our recently demonstrated single-emitting-layer white organic light-emitting diode (WOLED) to realize an extremely high-efficiency tandem WOLED. This stacked device achieves maximum forward viewing current efficiency of 110.9 cd/A and external quantum efficiency of 43.3% at 1 mu A/cm(2) and emits stable white light with Commission Internationale de L'Eclairage coordinates of (0.34, 0.41) at 16 V. It is noted that the combination of effective single units and CGL is key prerequisite for realizing high-performance tandem WOLEDs.

Conversion process of the dominant electroluminescence mechanism in a molecularly doped organic light-emitting device with only electron trapping

In this work, the detailed conversion process of the dominant electroluminescence (EL) mechanism in a device with Eu(TTA)(3)phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) doped CBP (4,4(')-N,N-'-dicarbazole-biphenyl) film as the emitting layer was investigated by analyzing the evolution of carrier distribution on dye and host molecules with increasing voltage. Firstly, it was confirmed that only electrons can be trapped in Eu(TTA)(3)phen doped CBP. As a result, holes and electrons would be situated on CBP and Eu(TTA)(3)phen molecules, respectively, and thus creates an unbalanced carrier distribution on both dye and host molecules. With the help of EL and photoluminescence spectra, the distribution of holes and electrons on both Eu(TTA)(3)phen and CBP molecules was demonstrated to change gradually with increasing voltage. Therefore, the dominant EL mechanism in this device changes gradually from carrier trapping at relatively low voltage to Forster energy transfer at relatively high voltage.

Photoluminescence and electroluminescence properties of a samarium complex Sm(TTA)(3)phen

The photoluminescence (PL) and electroluminescence (EL) properties of a samarium complex Sm(TTA)(3)phen (TTA = 2-thenoyltri-fluoroacetonate, phen = 1, 10-phenanthroline) were investigated. The results show that Sm(TTA)3phen could be used as promising luminescent and electron transporting material in the electroluminescent devices. The difference between PL and EL spectra was noticed and discussed. Besides, it is noteworthy that the choice of the hole transporting layer (HTL) showed significant effect on the device performance, which was explained by the low-lying highest occupied molecular orbit (HOMO) level of Sm(TTA)3phen and the different hole injection barrier at the HTL/EML (emitting material layer) interface.

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.

Ligand effect on the performance of organic light-emitting diodes based on europium complexes

A series of europium complexes were synthesized and their electroluminescent (EL) characteristics were studied. It was found by comparison that the different substituted groups, such as methyl, chlorine, and nitryl, on ligand 1,10-phenanthroline affect significantly the EL performance of devices based on these complexes. The more methyl-substituted groups on ligand 1,10-phenanthroline led to higher device efficiency. A chlorine-substituted group showed the approximate EL performance as two methyl-substituted groups, whereas a nitryl substituent reduced significantly the EL luminous efficiency. However, beta-diketonate ligand TTA and DBM exhibited similar EL performance. The improved EL luminous efficiency by proper substituted groups on the 1, 10-phenanthroline was attributed to the reduction of the energy loss caused by light hydrogen atom vibration, as well as concentration quenching caused by intermolecular interaction, and the match of energy level between the ligand and Eu3+.