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1.
The microporous metal‐organic framework Cd 2(ABTC)(H 2O)(DMA) 2 · H 2O · 3DMA ( 1 ) (H 4ABTC = 3, 3′,5, 5′‐azobenzenetetracarboxylic acid; DMA = N, N′‐dimethylacetamide) was prepared by solvothermal reaction and characterized. X‐ray structure analysis revealed that compound 1 is a three‐dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4‐connected rectangular ABTC 4– units with 4‐connected tetrahedral dinuclear Cd 2(CO 2) 4(H 2O)(DMA) 2 secondary building units (SBUs). The solid‐state excitation‐emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm. 相似文献
2.
A series of 3D d–f heterometallic coordination polymers, {[ Ln2Zn(Pzdc) 4(H 2O) 6] · 2H 2O} n [ Ln = La ( 1 ), Pr ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Gd ( 6 ), Tb ( 7 ), Dy ( 8 )] (H 2Pzdc = 2,3‐pyrazine dicarboxylic acid), were synthesized by one‐pot reactions under hydrothermal conditions. X‐ray crystallographical analysis and powder X‐ray diffraction analysis reveal that the complexes 1 – 8 are isostructural and adopt a multi‐parallel quadrilateral channel network structure with {4.6 · 2} 2{4 · 2.6 · 2.8 · 2}{6 · 3}2{6 · 5.8} 2 topology, in which the central LnIII ion is nine‐coordinate by four oxygen atoms and two nitrogen atoms from four ligands and three oxygen atoms from three coordinated H 2O molecules and the central Zn II ion is six‐coordinate by four oxygen atoms and two nitrogen atoms from four ligands. Moreover, the photophysical properties related to the electronic transition for complexes 4 , 5 , 7 , and 8 were investigated by the excitation and emission spectra as well as the emission lifetimes. 相似文献
3.
Two europium trifluoroacetate complexes, Eu(CF 3COO) 3·phen ( 1 ) and Eu(CF 3COO) 3·bpy ( 2 ) (where phen=1,10‐phenanthroline, bpy=2,2′‐bipyridine), were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) spectroscopy and thermogravimetric analysis (TA). Single‐crystal X‐ray structure has been determined for the complex [Eu 2(CF 3COO) 6·(phen) 3·(H 2O) 2]·EtOH. The crystal structure of [Eu 2(CF 3COO) 6·(phen) 3·(H 2O) 2]·EtOH shows that two different coordination styles with europium ions coexist in the same crystal and have entirely different coordination geometries and numbers. This crystal can be considered as an 1:1 adduct of [Eu(CF 3COO) 3·(Phen) 2·H 2O]·EtOH (9‐coordination part) and Eu(CF 3COO) 3·phen·H 2O (8‐coordination part). The excitation spectra of the two complexes demonstrate that the energy collected by "antenna ligands" is transferred to Eu 3+ ions efficiently. The room‐temperature PL spectra of the complexes are composed of the typical Eu 3+ ions red emission, due to transitions between 5D 0→ 7F J(J=0→4). The lifetimes of 5D 0 of Eu 3+ in the complexes were examined using time‐resolved spectroscopic analysis, and the lifetime values of Eu(CF 3COO) 3·phen and Eu(CF 3COO) 3·bpy were fitting with bi‐exponential (2987 and 353 µs) and monoexponential (3191 µs) curves, respectively. In order to elucidate the energy transfer process of the europium complexes, the energy levels of the relevant electronic states had been estimated. The thermal analyses indicate that they are all quite stable to heat. 相似文献
4.
Triboluminescence of Ln(acac) 3·H 2O (Ln = Tb, Eu, Pr, Ce, Gd) was found. The UV radiation was detected for the first time as narrow bands caused by the emission of the adsorbed N 2* molecules (transitions 3∏ u → 3∏ g) in the study of triboluminescence of lanthanide compounds. The emission of Ln 3+* (ionic triboluminescence) was observed only for Tb 3+* (λ max/nm: 490 ( 5D 4- 7F 6), 545 ( 5D 4- 7F 5), 580 ( 5D 4- 7F 4)) and Eu 3+* (λ?max/nm: 613, 614 ( 5D 2- 7F 3)). The generation of N 2* occurs due to the energy of electric fields appeared upon the destruction of crystalline samples of Ln(acac) 3·H 2O. The Tb 3+* and Eu 3+* ions are formed due to the energy transfer from the triplet level of the ligand (acacT 1), which is excited by the light emitted from the N 2* molecule. 相似文献
5.
Two metal coordination polymers, namely {[Co(1,3-BIP)(OBA)]·0.5H2O}n (SNUT-1) and [Co2(µ-η1:η1-O2)(1,3-BIP)2(PMA)]n (SNUT-2), where 1,3-BIP?=?1,3-bis(imidazol)propane, H2OBA?=?4,4′-oxybis(benzoate) and H4PMA?=?benzene-1,2,4,5-tetracarboxylic acid, were prepared by hydrothermal methods. Single-crystal X-ray analysis revealed that the structure of SNUT-1 consists of a 3D?→?3D twofold interpenetrating network that can be described as a 4-connected uninodal net with (65·8) topology. The structure of SNUT-2 consists of a 3D framework which can be described as a (4,5)-connected binodal net with (42·63·84·10) (33·42·5) topology. The gas adsorption properties of SNUT-1 and photocatalytic activity of SNUT-2 for the degradation of Rhodamine B have been explored. 相似文献
6.
The polarized Raman spectra of La(C 2H 5SO 4) 3·9H 2O, La(C 2H 5SO 4) 3·9D 2O and KC 2H 5SO 4 crystals have been observed from 30 to 4000 cm −1 at room temperature. The observed bands have experimentally been classified into each Raman-active symmetry species. From the far-infrared spectra from 30 to 300cm −1 of La(C 2H 5SO 4) 3· 9H 2O, the absorption bands of the infrared-active E 1u species have also been obtained. The vibrational assignment for the ethylsulfate group has been made by comparing the spectra of La(C 2H 5SO 4) 3·9H 2O and La(C 2H 5SO 4) 3·9D 2O with those of KC 2H 5SO 4 and using a group-theoretical consideration. 相似文献
7.
The intensities of the Δ M = ± 1 component of the 7f o→ 5D 2 transition in D 3 complexes containing the [ EuO 9] cluster, and of other d-d or f-f transitions in D 3 complexes with the yz- and xz-components of the electric quadrupole as the leading moment, are found to be dependent upon the polarizability anisotropy of the ligands. The expectation is supported by determinations of the single-crystal absorption intensities of Na 3 [Eu(diglycollate) 3]·2NaClO 4·6H 2O and [Eu(H 2O) 9] (C 2H 5SO 4) 3. 相似文献
8.
The solubilization of an europium (III) β-diketonate chelate in aqueous medium and the changes in its photophysical properties upon its inclusion into an α-cyclodextrin hydrophobic cavity are described. The complex [Eu(tta) 3·(H 2O) 2] (tta = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione) was synthesized, characterized, and incorporated into the hydrophobic cavity by stirring in an α-cyclodextrin aqueous solution. The inclusion was confirmed by 1H NMR, and the stoichiometry of association was obtained by the Job method. The maximum in the excitation spectrum of the α-CD inclusion compound in aqueous solution was shifted 28 nm compared with the maximum of non α-CD complex. The emission spectrum of the association is similar to that of the free solid complex and displays the characteristic 5D 0 → 7F 0-4 Eu 3+ transitions. 相似文献
9.
Eight metal(II) complexes based on imidazo[4, 5‐f]‐1, 10‐phenanthroline (HIMP) and bridging dicarboxylato ligands such as 4, 4′‐biphenyldicarboxylic acid (H 2BPDC), 1, 4‐benzenedicarboxylic acid (H 2BDC), thiophene‐2, 5‐dicarboxylic acid (H 2TDC), and 2, 6‐naphthalenedicarboxylic acid (H 2NDC) were hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. Complexes 1 , 3 , 6 , and 7 are molecular dinuclear metal complexes. Complexes 2 , 4 , and 5 exhibit chain‐like structures. Compound 8 shows a novel 3D architecture, in which Zn II dimers are connected by four NDC 2– anions. In the metal(II) complexes, HIMP exhibits a similar chelating coordination mode. Different π ··· π stacking interactions are observed in the complexes. The emission of HIMP is completely quenched in complexes 1 – 4 due to the strong π ··· π stacking interactions in the structures. Complexes 5 – 8 exhibit different photoluminescence properties. Firstly, we quantitatively investigated the effect of the strong HIMP–HIMP stacking interactions on the emission quenching of HIMP in the metal complexes. It was found that a higher extent of π ··· π stacking interactions in the complexes resulted in a higher extent of the emission quenching of HIMP. The introduction of aromatic conjugated carboxylate groups into metal(II)‐HIMP complexes changed the extent of the strong π ··· π stacking interactions in the structures and thus the photoluminescence properties of the complexes. 相似文献
10.
Neutralized ion beam studies of the clusters NH 4·(NH 3) n and H 3O·(H 2O) n, n = 0–3, and their fully deuterated analogs are presented. Stabilization of the hypervalent monomer radicals is found to accompany solvation. Cluster stability is found to decrease with increasing size. Reasons for this observation are discussed. Internally excited clusters are found to stabilize efficiently through the sequential loss of structural units (NH 3 or H 2O). The mixed isotopic dimer clusters (D 218O)·D·(D 216O) and (HDO)·D·(D 2O) are also investigated. Presence of the D 316O radical structural unit is found to be crucial to dimer stability. This is consistent with the results of earlier investigations involving the monomer which showed the surprising lifetime progression τ(D 316O) ≫; τ(D 318O) ⩾ τ(H 316O). 相似文献
11.
The equilibrium solubility of CsCl-CeCl3-HCl(11%)-H2O qua-ternary system at 25℃ has been determined by the physicchemical analysis method ,and the phase diagram was plotted, Two new double salts 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O obtained from the complicated system were identified and characterized by XRD,TG-DTA ,DSC,UV and fluorescence spectroscopy, Studies on the fluorescence excitation and emission show that 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O have upconversion luminescence of infrared-visible range,and the upconversion emission intensity increases with the increase of ratio of CeCl3 in CsCl. 相似文献
12.
Charge-transfer salts [Co(C 5H 5) 2][M(dpt) 2] (M = Ni and Pt; dpt = cis-1,2-diphenylethene-1,2-dithiolate) were synthesized and crystallographically characterized. [Co(C 5H 5) 2][Ni(dpt)2] crystallizes in the monoclinic space group C2/ c with a = 25, 607(3) Å, b = 9.4151(11) Å, c = 14.407(4) Å, β = 101.373(22)°, V = 3405.3(10) Å 3 and Z = 4. [Co(C 5H 5) 2][Pt(dpt) 2] belongs to the triclinic space group $ {\rm P}\bar 1 $ with a = 9.4666(11) Å, b = 13.9869(12) Å, c = 14.2652(9) Å, α = 99.983(6)°, β = 90.034(7)°, γ = 109.751(7)°, V = 1747.2(3) Å 3 and Z = 2. Both structures consist of ··· D +A ?D +A ?D +A ? ··· linear chains with the local C 5 axis of the eclipsed [Co(C 5H 5) 2] + cation parallel to the best MS 4 plane of the [M(dpt) 2] ? anion. Magnetic susceptibility measurements show that χ M T values of the complexes [Co(C 5H 5) 2][M(dpt) 2] (M = Ni, Pd, and Pt) remain nearly constant in the temperature range 15–300 K, but decrease rapidly with further decreasing of temperature, indicating weak antiferromagnetic interactions at low temperatures. 相似文献
13.
The rate constants 〈σ · υ〉 for collisional de-excitation of the metastable 5 D states of Ba + ions have been determined in an ion trap experiment. The D-states are selectively populated by pulsed laser excitation of the 6 P 1/2 or 6 P 3/2 state and the decay at different background pressures is monitored by the change in fluorescence intensity of the excited ions. From the pressure dependence of the decay constants we calculate the de-excitation rate constants for different collision partners, averaged over the velocity distribution of the trapped ion cloud. For He, Ne, H 2 and N 2 we obtain in the c.m. energy range of 0.1–0.5 eV: 〈σ·υ〉 (He)=3.0±0.2·10 ?13cm 3/ s, 〈σ·υ〉 (Ne)=5.1±0.4·10 ?13cm 3/ s, 〈σ·υ〉 (H 2)=3.7±0.3·10 ?11cm 3/ s, 〈σ·υ〉 (N 2)=4.4±0.3·10 ?11cm 3/ s. The results can be understood qualitatively by a consideration of the ion-atom and ion-molecules interaction potential. 相似文献
14.
[Tb 2(1,2-pdoa) 3 · 6H 2O] · H 2O ( 1) and [La(1,2-pdoa)(1,2-H 2pdoa)(OH) · H 2O] · 5H 2O ( 2) (1,2-H 2pdoa = 1,2-phenylenedioxydiacetic acid) have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 is a binuclear molecule in which one 1,2-pdoa ligand is a tetradentate bridge linking two Tb 3+ ions, the other two 1,2-pdoa ligands bond Tb1 3+ and Tb1A 3+ via tetradentate chelating coordination. Tb 3+ is nine-coordinate by six oxygens of 1,2-pdoa and three waters. Complex 2 is mono-nuclear with La 3+ ten-coordinate by eight oxygens of two 1,2-pdoa, one hydroxide and one water. 1,2-Pdoa is tetradentate chelating with La 3+ ion. The packing diagrams of 1 and 2 show supramolecular networks via H-bonds. The fluorescence spectrum of 1 shows characteristic emission of Tb 3+ with 5D 4 → 7F j (j = 6–3) transitions. 相似文献
15.
Three new extended iron‐containing heteropolytungstates were synthesized and structurally characterized: K 6[{Fe II(H 2O) 4} 2(H 2W 12O 42)]·15H 2O ( 1 ), Na 5[{Fe(H 2O) 3} 2{Fe(H 2O) 4} 0.5(H 2W 12O 42)]·30H 2O ( 2 ) and (H 3O) +2[{Fe(H 2O) 4Fe(H 2O) 3} 2(H 2W 12O 42)]·20H 2O ( 3 ). 1 and 3 crystallize in the monoclinic system, space group P2 1/n with a = 14.9967(5), b = 10.3872(3), c = 18.8237(6)Å, β = 93.407(1)°, V = 2927.1(2)Å 3 and D c = 4.151 g cm —3 for 1 , and space group P2 1/c with a = 12.1794(4), b = 22.4938(4), c = 11.6941(3) Å, β = 105.731(2)°, V = 3083.7(1) Å 3, and D c = 4.043 g cm —3 for 3 . 2 is triclinic, space group P1¯, with a = 12.121(2), b = 12.426(3), c = 13.247(3)Å, α = 68.33(3), β = 71.33(3), γ = 71.44(3)°, V = 1710.7(6)Å 3 and D c = 3.735 g cm —3. In all cases, the structures are based on paradodecatungstate polyoxoanions, which are linked by iron ions into chains, layers and a three‐dimensional structure for 1 , 2 and 3 , respectively. 相似文献
16.
The reaction of the aryl‐oxide ligand H 2L [H 2L = N, N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐ N‐(2‐pyridylmethyl)amine] with CuSO 4 · 5H 2O, CuCl 2 · 2H 2O, CuBr 2, CdCl 2 · 2.5H 2O, and Cd(OAc) 2 · 2H 2O, respectively, under hydrothermal conditions gave the complexes [Cu(H 2L 1) 2] · SO 4 · 3CH 3OH ( 1 ), [Cu 2(H 2L 2) 2Cl 4] ( 2 ), [Cu 2(H 2L 2) 2Br 4] ( 3 ), [Cd 2(HL) 2Cl 2] ( 4 ), and [Cd 2(L) 2(CH 3COOH) 2] · H 2L ( 5 ), where H 2L 1 [H 2L 1 = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H 2L 2 [H 2L 2 = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission. 相似文献
17.
Te(OH) 6 · 2Na 3P 3O 9 · 6H 2O, is hexagonal (P6 3/m) with a = 11,67(1), c = 12,12(1) Å, Z = 2 and D x = 2,225 g/cm 3. Te(OH) 6 · K 3P 3O 9 · 2H 2O, is monoklin (P2 1/c) with a = 19,61(5), b = 7,456(1), c = 14,84(6) Å, = 108,01(4), Z = 4 and D x = 2,506 g/cm 3. Both compounds are the first examples of phosphate tellurates in which the anion phosphate is condensed to the ring anion P 3O 9. As in phosphate tellurates already described the phosphate groups are independent of the TeO 6 octahedra. 相似文献
18.
High quality LiLuF 4 single crystals doped with various Pr 3+ ions were synthesized by a vertical Bridgman method in completely sealed platinum crucibles. The excitation spectra spans from 420 nm to 500 nm. The prepared single crystals exhibit a blue band at 480 nm ( 3P 0→ 3H 4), a green band at 522 nm ( 3P 1→ 3H 5), and a red band at 605 nm ( 1D 2→ 3H 4) when excited at 446 nm; their corresponding average lifetimes are 38.5 μs, 37.3 μs, and 36.8 μs, respectively, which are much longer than those in oxide single crystals. The effects of excitation wavelength and doping concentration on emission intensities and chromaticity coordinates are investigated. The optimal Pr 3+ concentration is confirmed to be 0.5%. The temperature dependent emission shows that the emission intensity constantly decreases with the increase of temperature from 298 K to 443 K due to the enhancement of non-radiative quenching at high temperature. The 3P 0→ 3H 4 transition is the most vulnerable to temperature, followed by the 3P 1→ 3H 5 transition and 1D 2→ 3H 4 transition. 相似文献
19.
Light emission from aqueous solutions of HClO 4 containing U 4+ and S 2O 8 2? has been observed. The emitter of chemiluminescence (CL) is the electron-excited uranyl ion ( *UO 2 2+ ), the product of U 4+ oxidation. A hundredfold decrease in the HClO 4 concentration (from 1 to 0.01 mol L ?1) results in a 250-fold increase in the reaction rate constant, a 5000-fold increase in the initial CL (from 4·10 5 to 2·10 9 photon s ?1), a more than tenfold increase in the CL yield (from 5.6·10 ?8 to 1.6·10 ?6), and a 200-fold increase in the excitation yield of UO 2 2+ (from 6·10 ?6 to 1.3·10 ?3). The kinetic isotope effect of the reaction has been studied. The value for the ratio of the rate constants k H/ k D=2.1 has been determined by extrapolation to the 100% degree of deuteration of 0.1 M perchloric acid. The peculiarities of the chemiluminescence stage in the reaction of U 4+ oxidation in solutions of potassium persulfate were explained by the participation of the products of hydrolysis of the U 4+ aqua ion (UOH 3+ and U(OH) 2 2+ ), whose relative fraction increases as the HClO 4 concentration decreases. 相似文献
20.
The non‐ionic europium(III) complex [Eu(TTA) 3·DAF]·0.5C 7H 8 (TTA = 2‐thenoytrifluoroacetonate, DAF = 4, 5‐diazafluoren‐9‐one) was synthesized. The structural determination has been carried out. DAF coordination induces the both excitation spectra in the solid state and solution having a red shift and sensitizes Eu 3+ luminescence under visible light excitation. 相似文献
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