Near-infrared luminescent Nd~(3+)/Yb~(3+)-codoped metal-organic framework for ratiometric temperature sensing in physiological range

Self-calibrating luminescent thermometry employing luminescence within the optical transparency windows provides a promising prospect for temperature measurement in the biological fields.In this work,a new Nd~(3+)/Yb~(3+)-codoped metal-organic framework Nd_(0.95)Yb_(0.05)BPTC showing threedimensional anionic network,obtained by reacting ligand [1,1'-biphenyl]-3,3',5,5'-tetracarboxylic acid(H_4BPTC) with Nd~(3+) and Yb~(3+) ions under solvothermal conditions,is reported.Upon 808 nm photoexcitation,Nd_(0.95)Yb_(0.05)BPTC simultaneously emits the characteristic near-infrared luminescence of Nd~(3+) and Yb~(3+) ions based on the efficient energy transfer from Nd~(3+) to Yb~(3+) ions.In addition,the emission intensity ratio of Yb~(3+) and Nd~(3+) shows good exponential-like response to temperature in the physiological range of 293-323 K.The feature properties of Nd_(0.95)Yb_(0.05)BPTC include near-infrared absorption and emission,favorable temperature sensitivity and accurate temperature uncertainty,as well as good chemical stability,making such system useful in biomedical applications.     

Ionic liquids as novel spectroscopic solvents for Eu（III）-containing complex

Novel soft materials,Eu(III)-containing complex dissolved in [C8mim][X](X=Cl-,PF6-and Tf2N-) ionic liquids,were synthesized.FT-IR and elementary analysis of complex proved that the molecular formula is [C8mim][Eu(TTA)4].The complex and ionic liquids had highthermal stability according to TGA.The photoluminescence spectra showed that the [C8mim][Eu(TTA)4] exhibited typical red emission deriving from 5D0-7F2 transition.After dissolving the complex in [C8mim][X](X=Cl-,PF6-and Tf2N-) ionic liquids,the luminescence intensitydecreased in the following order:[C8mim][Tf2N]≈[C8mim][PF6 ]>[C8mim][Cl].This was because Tf2N-and PF6-anions had larger molecularvolume and weaker coordination ability than Cl-.     

Characterization,crystal structure and luminescence properties of a new europium（Ⅲ） complex with macrocyclic ligand derived from 2,6-diformyl-4-methylphenol and diethylenetriamine

The title compound （13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 （29）,2,9,11,13,15（30）, 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30）-bis （nitrato-O,O＇）-europium （Ⅲ） nitrate hydrate （[EuL（NO3）2]（NO3）·H2O, L denotes the macrocyclic ligand） was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 （4） nm, b=1.4302（3） nm, c=1.9584（3） nm, β=91.654（5）°, M=818.60, V=6.651（2） nm^3, Z=8, D=1.635 g/cm, F（000）=3312, R=0.0542, wR=0.1045. The central ion Eu^3＋ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3＋ ion.     

A novel fluorescent sensor for Al~(3+) and Zn~(2+) based on a new europium complex with a 1,10-phenanthroline ligand

A new europium complex Eu(tta)₃Li(la)based on 1,10-phenanthroline derivative(Li=(2-(3,5-dimethoxyphenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline),tta=2-thenoyItrifluoroacetone)was designed and synthesized.Its structure was characterized by¹H and¹³C NMR,elemental analysis,UV-vis,fluorescence spectra and single crystal X-ray diffraction.The crystal of the complex la belongs to monoclinic system with the space group P2_1/n.The europium complex la in the solid and in the solution displays the typical emission of Eu(III)ion centered at 612 nm as a result of the electric dipole transition(⁵D₀-?⁷F₂).It exhibits high quantum yield(20.42%),long lifetime(0.29 ms)and good CIE color coordinate(0.67,0.33)in solid.In addition,the complex shows high sensitivity and selectivity towards Al³⁺and Zn²⁺in methanol solution which can be attributed to the Al³⁺/Zn²⁺cation instead of Eu³⁺in the complex la.The LODs for Al³⁺and Zn²⁺were calculated to be 5.880×10^-7and 7.678×10^-8mol/L,respectively.Besides,the additions of Al³⁺and Zn²⁺express remarkable color changes from red to bright blue and ivory that can be clearly observed by the naked eye respectively.     

Temperature sensing behavior of Tm~(3+):~1G_4(a),~1G_4(b) in oxyfluoride glass ceramics containing BaYb_xY_(1-x)F_5 nanocrystals

Tm~(3+)-doped transparent oxyfluoride glass ceramics containing BaYb_xY((1-x))F_5 nanocrystals were prepared via high temperature solid phase melting method,of which up-conversion emission is achieved by the Yb~(3+)-mediated energy transfer process.The required photon number of Tm~(3+)ions emissions in BaYb_xY_((1-x))F_5 nanocrystals was calculated through the luminescence spectra,revealing the strong dependence of energy transfer mechanism on Yb~(3+)ions concentration.Meanwhile,based on the fluore scence intensity ratio technology,the effect of different energy transfer mechanism on the temperature sensitivity was investigated by the temperature-dependent luminescence intensity of thermally coupled energy levels of Tm~(3+):~1G_4(a),~1G_4(b).The obtained sensitivity decreases with the increase of Yb~(3+)ions content,which is mainly attributed to the changes in photon absorption process of Tm~(3+):~1G_4(b).     

Sensitivity of a solid Eu(III) complex towards acetonitrile vapor: Structural and spectroscopic characterization

The Eu(III) nitrate complex of the meso- N,N′-bis(2-pyridylmethylene)-1,2-(R,S)-cyclohexanediamine ligand was synthesized and characterized by single crystal and powder X-ray diffraction. The crystal lattice of the complex is capable of absorbing and desorbing selectively acetonitrile molecules, at 293 K upon an acetonitrile vapor pressure of ∼0.1 × 10⁵ Pa. This process, which is partially reversible, can be easily followed by both powder X-ray diffraction (P-XRD) and Eu(III) luminescence spectroscopy. The acetonitrile molecule, located in the outer coordination sphere of the metal ion, does not affect the radiative transition probability of ⁵D₀ level of Eu(III) and also it does not activate further non-radiative channels from this level. On the other hand, this molecule is capable of affecting the energy position and intensities of the crystal field components of the ⁵D₀→⁷F₂ transition. The complex in solid form can be considered a promising material for the optical sensing of acetonitrile vapors.     

One pot synthesis of TiO2:Eu3+ hierarchical structures as a highly specific luminescent sensing probe for the visualization of latent fingerprints

In the present work, TiO₂:Eu³⁺ (1 mol%–11 mol%) nano powders (NPs) were prepared via a facile one-pot hydrothermal method by using Epigallocatechin Gallate (EGCG) as bio-surfactant. The optimized TiO₂:Eu³⁺ (5 mol%) NPs can be used as fluorescent labeling agent for visualizing of latent fingerprints (LFPs) on various porous and non-porous surfaces. The obtained results exhibit well defined ridge details with high sensitivity, selectivity, and low background hindrance which show greater advantages as compared to conventional powders. We demonstrated the viability of high-performance security labels thorough excellent luminescence for practical anti-mimetic applications. Morphology of the prepared samples is highly dependent on pH, concentration of the bio-surfactant, temperature and time durations. Photoluminescence (PL) emission spectra exhibit intense red emission at ～ 615 nm due to electric dipole transition (⁵D₀→⁷F₂). Photometric (CIE and CCT) results clearly show the intense warm red emission of the optimized samples. Therefore, this work offers a superior and universal luminescent label, which can be applied to visualize miniature LFPs particulars for individualization and consequently display great prospective in forensic investigation.     

A novel Ga(Ⅲ)coordination complex as an efficient sensitizer for enhancing photocatalytic activity of TiO2/rGO nanocomposite

Narrow solar-light response range and rapid charges recombination are the main technical barriers in TiO₂ photocatalysis technology.To overcome these restrictions,in this work we synthesized a novel binuclear gadolinium(Ⅲ) coordination complex,[Gd₂(DPDB)₆(DMF)₆(H₂O2)](DPDB=[(4-dimethylamino)phenyldiazenyl] benzenesulfonate),which was used as an inorganic sensitizer for boosting the visible light-harvesting and quantum efficiency o...     

Synthesis and structure of a praseodymium (III) complex with carboxylate ligand: A thermal and spectroscopic study

One Pr(III) lanthanide ion complex was initially synthesized and characterized by TGA-DSC in air atmosphere, as well as characterized by CHN elemental analysis, defining the stoichiometric ratio as Pr(DMBz)₃. The gaseous products evolved during the thermal decomposition were also monitored in N₂ atmosphere employing TGA/FT-IR system. A crystal structure is obtained by state-of-the-art powder X-rays diffraction methods measured in conventional laboratory equipment and refined by the Rietveld method, which defined it as a monoclinic system of the space group P2₁/c with a polymeric crystal structure, [Pr(DMBz)₃]_n. FT-IR theoretical spectrum and time-dependent density functional theory (TD-DFT) were calculated from TGA-DSC and crystalline system data. The experimental and theoretical FT-IR spectra present a high correlation degree when the main stretching bands are compared, while the energy transfer (HOMO – LUMO) in their neighborhoods suggests the main contributions of the light-emitting states.