Ag@SiO2@Y2O3:RE3+（RE=Eu,Tb）核壳结构发光材料的制备与性能

采用均相沉淀法制备了Ag@SiO2@(Y,RE)(OH)CO3.H2O(RE=Eu,Tb)核壳结构微球,经过700℃焙烧后成功制备出Ag@SiO2@Y2O3:RE3+(RE=Eu,Tb)核壳结构发光材料。XRD谱图表明Ag核具有结晶良好的面心立方结构;SiO2层为无定型;Y2O3层为立方晶系。FTIR谱图表明核壳之间以化学键相结合。TEM照片表明合成了核壳结构的表面光滑的复合微球,分散良好,大小均匀,Ag核的粒径分布为50±20 nm;SiO2层的厚度为20～30 nm;Y2O3:RE3+(RE=Eu,Tb)层厚度约为125 nm。电子衍射图像表明Ag@SiO2@Y2O3:RE3+(RE=Eu,Tb)为多晶结构。UV-Vis光谱表明表面包覆使Ag离子的等离子体共振吸收峰发生了红移。荧光光谱表明Ag@SiO2@Y2O3:Eu3+具有Eu3+的特征红光发射,Ag@SiO2@Y2O3:Tb3+具有Tb3+的特征绿光发射,但是发光强度均比纯的Y2O3:RE3+有所减弱,说明贵金属的引入对稀土Y2O3:RE3+(RE=Eu,Tb)的发光起到了荧光猝灭的作用。     

NMR and electron paramagnetic resonance studies of [Gd(CH3CN)9]3+ and [Eu(CH3CN)9]2+: solvation and solvent exchange dynamics in anhydrous acetonitrile

Homoleptic acetonitrile complexes [Gd(CH(3)CN)(9)][Al(OC(CF(3))(3))(4)](3) and [Eu(CH(3)CN)(9)][Al(OC(CF(3))(3))(4)](2) have been studied in anhydrous acetonitrile by (14)N- and (1)H NMR relaxation as well as by X- and Q-band EPR. For each compound a combined analysis of all experimental data allowed to get microscopic information on the dynamics in solution. The second order rotational correlation times for [Gd(CH(3)CN)(9)](3+) and [Eu(CH(3)CN)(9)](2+) are 14.5 ± 1.8 ps and 11.8 ± 1.1 ps, respectively. Solvent exchange rate constants determined are (55 ± 15) × 10(6) s(-1) for the trivalent Gd(3+) and (1530 ± 200) × 10(6) s(-1) for the divalent Eu(2+). Surprisingly, for both solvate complexes CH(3)CN exchange is much slower for the less strongly N-binding acetonitrile than for the more strongly coordinated O-binding H(2)O. It is concluded that this exceptional behavior is due to the extremely fast water exchange, whereas the exchange behavior of CH(3)CN is more regular. Electron spin relaxation on the isoelectronic ions is much slower than on the O-binding water analogues. This allowed a precise determination of the hyperfine coupling constants for each of the two stable isotopes of Gd(3+) and Eu(2+) having a nuclear spin.     

A novel strategy for controllable emissions from Eu3+ or Sm3+ ions co-doped SrY2O4:Tb3+ phosphors

Trivalent rare-earth (RE) ions (Eu(3+), Tb(3+) and Sm(3+)) activated multicolor emitting SrY(2)O(4) phosphors were synthesized by a sol-gel process. The structural and morphological studies were performed by the measurements of X-ray diffraction profiles and scanning electron microscope (SEM) images. The pure phase of SrY(2)O(4) appeared after annealing at 1300 °C and the doping of RE ions did not show any effect on the structural properties. From the SEM images, the closely packed particles were observed due to the roughness of each particle tip. The photoluminescence (PL) analysis of individual RE ions activated SrY(2)O(4) phosphors exhibits excellent emission properties in their respective regions. The Eu(3+) co-activated SrY(2)O(4):Tb(3+) phosphor creates different emissions by controlling the energy transfer from Tb(3+) to Eu(3+) ions. Based on the excitation wavelengths, multiple (green, orange and white) emissions were obtained by Sm(3+) ions co-activated with SrY(2)O(4):Tb(3+) phosphors. The decay measurements were carried out for analyzing the energy transfer efficiency and the possible ways of energy transfer from donor to acceptor. The cathodoluminescence properties of these phosphors show similar behavior as PL properties except the energy transfer process. The obtained results indicated that the energy transfer process was quite opposite to the PL properties. The calculated CIE chromaticity coordinates of RE ions activated SrY(2)O(4) phosphors confirmed the red, green, orange and white emissions.     

Rb2REGaSi4O12 (RE = Y, Eu, Gd, Tb): luminescent mixed-anion double layer silicates containing chains of edge-sharing REO7 pentagonal bipyramids

Four new rare earth gallosilicates, Rb 2REGaSi4O12 (RE = Y, Eu, Gd, and Tb, denoted as REGS-1), have been synthesized under high-temperature, high-pressure hydrothermal conditions and characterized by single-crystal X-ray diffraction. They are the first examples of rare earth gallosilicates that contain individually occupied tetrahedral Ga(3+) and Si(4+) centers. The unique structure is formed of two 1D and one 2D substructural units: unbranched achter single chains which are seldom observed in silicates, the PaCl 5-type infinite chains formed of edge-sharing REO7 petagonal bipyramids and the unprecedented mixed-anion double layers with the composition [GaSi4O12]. The photoluminescence properties of EuGS-1 and TbGS-1 have been studied. The Y(3+) ion in YGS-1 can be partially replaced by Eu(3+) and Tb(3+) to yield luminescent materials.     

Preparation of Gd(2)O(3) : Eu(3+) and Gd(2)O(2)S : Eu(3+) phosphor fine particles using an emulsion liquid membrane system

Size- (submicrometer-sized) and morphology- (spherical) controlled composite Gd-Eu oxalate particles were prepared in an emulsion liquid membrane (water-in-oil-in-water emulsion) system. The oxalate particles thus prepared were calcined in air to obtain Gd(2)O(3) : Eu(3+) phosphor particles and in sulfur atmosphere to obtain Gd(2)O(2)S : Eu(3+) phosphor particles. These submicrometer-sized spherical phosphor particles showed photoluminescence properties with emission peak at 614 nm for Gd(2)O(3) : Eu(3+) and 628 nm for Gd(2)O(2)S : Eu(3+).     

The effects of Gd3+ substitution on the crystal structure, site symmetry, and photoluminescence of Y/Eu layered rare-earth hydroxide (LRH) nanoplates

Well crystallized nanoplates of the (Y(0.95-x)Gd(x)Eu(0.05))(2)(OH)(5)NO(3)·nH(2)O ternary layered rare-earth hydroxides (LRHs), synthesized hydrothermally, have been investigated with emphasis on the effects of Gd(3+) substitution for Y(3+) on the structural features and optical properties. Characterizations of the materials were achieved by the combined techniques of XRD, FT-IR, TEM, DTA/TG, and optical spectroscopies. The results showed that Gd(3+) substitution leads to linearly expanded ab plane, shortened interlayer distance (c/2), and reduced hydration (smaller n value) of the crystal structure. As a consequence, the Ln(3+) partially shifts from the C(4v) to C(1) site symmetries and thus leads to systematically altered photoluminescence behaviors. Under the (7)F(0)→(5)L(6) transition excitation of Eu(3+) at 394 nm, both the (5)D(0)→(7)F(2) to (5)D(0)→(7)F(4) and the 595 nm (5)D(0)→(7)F(1) to 590 nm (5)D(0)→(7)F(1) intensity ratios linearly increase towards a higher Gd(3+) content. The incorporated Gd(3+) cations selectively sensitize emission from the C(1)-site Eu(3+) and produce a new charge transfer (CT) excitation band at ～254 nm. With this, the desired 615-nm red emission is obtainable either under intra-4f(6) transition excitation of Eu(3+) or by exciting the CT band. The materials have similar fluorescence lifetimes of 0.85 ± 0.05 ms for the 615-nm emission, irrespective of the Gd(3+) content and excitation wavelength.     

Effect of surface modification on photoluminescence properties of Y3Al5O12:Ce3+, Gd3+ nano-phosphors

In this study, a series of Y(3)Al(5)O(12):Ce(3+), Gd(3+) nano-phosphors were prepared using a simply wet chemical process with polyvinyl pyrrolidone as a modifier. The crystal and bonding structures of Y(3)Al(5)O(12):Ce(3+), Gd(3+) nano-phosphors prepared with different weight percentages of polyvinyl pyrrolidone were characterized by X-ray diffractometry and infrared spectrometry. The decomposition process of dried precursor gel with adding 1.37 wt% polyvinyl pyrrolidone was investigated by differential thermal and thermogravimetric analysis. The effect of surface modification on photoluminescence properties for the samples was studied. The results show that the steric hindrance effect of polyvinyl pyrrolidone leads to high dispersion and good crystallinity of Y(3)Al(5)O(12):Ce(3+), Gd(3+) nano-phosphors prepared with adding a proper weight percentages of polyvinyl pyrrolidone. Adding polyvinyl pyrrolidone is beneficial for the photoluminescence enhancement of the samples, which is attributed to the promotion of the incorporation of Ce(3+) and Gd(3+) into the Y(3)Al(5)O(12) nanocrystal and the surface passivation of the nano-particles by the polyvinyl pyrrolidone molecules.     

Bifunctional Mixed-Lanthanide Cyano-Bridged Coordination Polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), Tb(3+)/Sm(3+))

A new family of mixed-lanthanide cyano-bridged coordination polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (where Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), and Tb(3+)/Sm(3+)) containing two lanthanide and one transition metal ions were obtained and characterized by X-ray diffraction, photoluminescence spectroscopy, magnetic analyses, and theoretical computation. These compounds are isotypical and crystallize in the tetragonal system P4/nmm forming two-dimensional grid-like networks. They present a magnetic ordering at low temperature and display the red Eu(3+) ((5)D(0) → (7)F(0-4)) and green Tb(3+) ((5)D(4) → (7)F(6-2)) characteristic photoluminescence. The Tb(0.5)Eu(0.5)(H(2)O)(5)[W(CN)(8)] compound presents therefore green and red emission and shows Tb(3+)-to-Eu(3+) energy transfer.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

共沉淀法合成稀土正磷酸盐(La,Gd)PO4:RE3+(RE=Eu,Tb)及其真空紫外光谱特性

采用共沉淀法制备了稀土正磷酸盐荧光粉(La,Gd)PO4:RE3+(RE=Eu,Tb).红外光谱分析发现GdPO4的红外光谱吸收峰与LaPO4一致,只是峰位向高波数方向移动.(La,Gd)PO4:RE3+的真空紫外光谱特性研究表明,Gd3+在能量传递过程中起中间体作用.XPS研究揭示,LaPO4的价带由O2-的2p能级构成,而GdPO4的价带则是由O2-的2p能级和Gd3+的4f能级共同构成.     

3D flower-like Y(2)O(3):Eu(3+) nanostructures: template-free synthesis and its luminescence properties

In this work, a facile route using simple hydrothermal reaction and sequential calcinations to synthesize 3-dimensional flower-like Y(2)O(3):Eu(3+) nanoarchitectures without employing templates or matrix for self-assembly is presented. The flower-like nanostructures are composed of nanosheets with thickness of about 30 nm, which is verified by the field-emission electron microscopy (FESEM). Influencing factors such as the dosage of reactants, the solvent, and pH are systematically investigated. The time-dependent experiments indicate a self-assembly mechanism. This method is also applicable in the preparation of other lanthanide oxides. The PL spectra of the as-synthesized Y(2)O(3):Eu(3+) are systematically studied. Both the Eu(3+) concentration and the calcinations temperature have great effect on the luminescence intensity of (5)D(0)-(7)F(2) transition. The decay curve of the (5)D(0) transition shows that the lifetime of the as-obtained Y(2)O(3):Eu(3+) is about 2.4 ms.     

聚苯乙烯包覆Y_2O_3:Eu~(3 )颗粒及表征

采用柠檬酸表面修饰 Y2 O3:Eu3 颗粒 ,苯乙烯乳液聚合的方法 ,制备出核 -壳型的 Y2 O3:Eu3 /聚苯乙烯颗粒 .在 FTIR谱图上 ,羰基伸缩振动峰向低波数位移 ;在 XPS谱图上 ,Y3d5 / 2 的电子结合能向高能方向移动 ,表明柠檬酸和颗粒表面发生键合作用 .说明此过程符合吸附层媒介作用机理 :柠檬酸使颗粒表面变成两亲性 ,从而使苯乙烯可吸附在颗粒表面形成包覆无机核的乳液结构 .EDS谱图表明聚苯乙烯均匀地包覆在颗粒表面     

Sub-10 nm hexagonal lanthanide-doped NaLuF4 upconversion nanocrystals for sensitive bioimaging in vivo

By thermal decomposition in the presence only of oleylamine, sub-10 nm hexagonal NaLuF(4)-based nanocrystals codoped with Gd(3+), Yb(3+), and Er(3+) (or Tm(3+)) have been successfully synthesized. Sub-10 nm β-NaLuF(4): 24 mol % Gd(3+), 20 mol % Yb(3+), 1 mol % Tm(3+) nanocrystals display bright upconversion luminescence (UCL) with a quantum yield of 0.47 ± 0.06% under continuous-wave excitation at 980 nm. Furthermore, through the use of β-NaLuF(4):Gd(3+),Yb(3+),Tm(3+) nanocrystals as a luminescent label, the detection limit of <50 nanocrystal-labeled cells was achieved for whole-body photoluminescent imaging of a small animal (mouse), and high-contrast UCL imaging of a whole-body black mouse with a penetration depth of ~2 cm was achieved.     

Highly uniform and monodisperse Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres: solvothermal synthesis and luminescence properties

Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres were successfully prepared through a facile and mild solvothermal method followed by a subsequent heat treatment. X-ray diffraction (XRD) results demonstrate that all the diffraction peaks of the samples can be well indexed to the pure hexagonal phase of Gd(2)O(2)S. The energy dispersive spectroscopy (EDS), element analysis, and FT-IR results show that the precursors are composed of the Gd, Eu, O, S, C, H, and N elements. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that these spheres are actually composed of randomly aggregated nanoparticles. The formation mechanism for the Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres has been proposed on an isotropic growth mechanism. Under ultraviolet excitation, Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres show red and green emission corresponding to the (5)D(0)→(7)F(2) transition of the Eu(3+) ions and the (5)D(4)→(7)F(5) transition of the Tb(3+) ions. Furthermore, this synthetic route may have potential applications for fabricating other lanthanide oxysulfides.     

Vacuum Ultraviolet Excited Photoluminescence Properties of Y202S:Eu3+,Bi3+ Phosphor

As an Hg-free lamp using phosphor,the Bi3+ and Eu3+ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum uitraviolet(VUV) excitation were investigated.The VUV photolumineseent intensity of Y2O2S:Eu3+ was weak,however,considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S:Eu3+,Bi3+ systems.Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S:Eu3+,Bi3+ at 147 nm is mainly because the Bi3+ acts as a medium and effectively performs the energy transfer process: Y3+-O2→Bi3+→Eu3+,while the intense emission band at 172 nm is attributed to the absorption of the characteristic 1So-1P1 transition of Bi3+ and the direct energy transfer from Bi3+ to Eu3+.The Y2O2S:Eu3+,Bi3+ shows excellent VUV optical properties compared with the commercial (Y,Gd)BO3:Eu3+.Thus,the Y2O2S:Eu3+,Bi3+ can be a potential red VUV-excited candidate applied in Hg-free lamps for backlight of liquid crystal display.     

Effect of thermal annealing on the kinetics of rehydroxylation of Eu3+:La2O3 nanocrystals

Europium-doped lanthanum oxide (5 mol % Eu(3+):La(2)O(3)) was prepared by calcining europium-doped lanthanum hydroxide (5 mol % Eu(3+):La(OH)(3)) previously synthesized by a simple hydrothermal method. Interestingly, we observed different emission Eu(3+) signatures depending on the phase of the host (lanthanum oxide or hydroxide) by cathodoluminescence. Taking into account that lanthanum oxide easily rehydroxylates in air, for the first time, we report the use of cathodoluminiscence as a novel characterization technique to follow the lanthanum oxide rehydroxylation reaction versus time according to different annealing procedures. Additionally, differential thermal-thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction techniques were used to identify the phases formed from the Eu(3+):La(OH)(3) depending on temperature and to study the evolution of La(2)O(3) to La(OH)(3) versus time. The results showed that the higher the temperature and the longer the annealing time, the higher the resistance to rehydroxylation of the Eu(3+):La(2)O(3) sample.     

稀土配合物的研究(Ⅸ)——稀土元素与1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-(1,5)配合物的合成及性质

乙醇-水混合体系中合成了15种新的稀土元素的固态配合物,通过元素分析和化学分析确定了配合物的化学组成为RE_2(BPMPPD)_3·nH_2O和Ce(BPMPPD)_2·6H_2O(BPMPPD为1,5-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)戊二酮-[1,5]),对配合物的荧光光谱等性质进行了研究。     

Solid state white light emitting systems based on CeF3: RE3+ nanoparticles and their composites with polymers

A series of doped CeF(3): RE(3+) (RE(3+): Tb(3+), Eu(3+) and Dy(3+)) nanoparticles were synthesized, with the aim of obtaining a white light emitting composition, by a simple polyol route at 160°C and characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence. Uniformly distributed and highly water-dispersible rectangular nanoparticles (length ~15-20 nm, breadth ~5-10 nm) were obtained. The steady state and time resolved luminescence studies confirmed efficient energy transfer from the host to activator ions. Lifetime studies revealed that optimum luminescence is observed for 2.5 mol% Dy(3+) and 7.5 mol% Tb(3+). The energy transfer efficiencies (Ce(3+) to activators) were found to be 89% for CeF(3): Tb(3+) (7.5 mol%) nanoparticles and 60% for CeF(3): Dy(3+) (2.5 mol%) nanoparticles. Different concentrations of Tb(3+), Eu(3+) and Dy(3+) were doped to achieve a white light emitting phosphor for UV-based LEDs (light emitting diodes). Finally CeF(3), triply doped with 2.0 mol%Tb(3+), 4.5 mol% Eu(3+) and 3.5 mol% Dy(3+), was found to have impressive chromaticity co-ordinates, close to broad day light. The colloidal solutions of doped CeF(3) nanoparticles emitted bright green (Tb(3+)), blue (Dy(3+)) and white (triply doped) luminescence upon host excitation. Composites of poly methyl methacrylate (PMMA) and poly vinyl alcohol (PVA) were made with CeF(3): 5.0 mol%Tb(3+), CeF(3): 5.0 mol% Dy(3+) and triply doped white light emitting composition. The CeF(3)/PMMA (PVA) nanocomposite films, so obtained, are highly transparent (in the visible spectral range) and exhibit strong photoluminescence upon UV excitation.     

Eu3+:Y2O3 microspheres and microcubes: a supercritical synthesis and characterization

A new approach that uses mixed supercritical solvents of water/1-propanol and water/methanol (400 °C, 40 MPa) to prepare morphology-controlled precursor materials in a very short reaction time, such as 10 min, followed by calcinations has been developed to form Eu(3+):Y(2)O(3) microspheres of 2-3 μm in diameter or microcubes of 2-3 μm in side length, respectively. Eu(3+):Y(2)O(3) microspheres and microcubes exhibited strong red emission at 610 nm corresponding to (5)D(0) → (7)F(2) transition. The highest photoluminescence emission was obtained for the microspheres after calcination at 1000 °C for 1 h in air.     

Syntheses,crystal structures,and luminescent properties of lanthanide complexes with tripodal ligands bearing benzimidazole and pyridine groups

Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L(1)) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L(2)), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO(4))(3) (series A), [LnL(1)(Antipy)Cl(H(2)O)(2)]Cl(2)(H(2)O)(2) (series B), and [LnL(2)(NO(3))(3)] (series C). The nitrate salt of the free ligand H(2)L(1).(NO(3))(2) and six complexes were structurally characterized: Pr(3+)A, Y(3+)A, Eu(3+)B, Eu(3+)C, Gd(3+)C and Tb(3+)C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L(1) and L(2) exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl(-) dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO(3)(-) ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (3)LC level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L(1) and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.