Visible light-induced magnetization change of the cyano-bridged 3d-4f heterobimetallic

A visible light-induced magnetization change of the 3d-4f heterometallic, [Nd(DMF)₄(H₂O)₃(μ-NC)Co(CN)₅]·H₂O (DMF=N,N-dimethylformamide), is observed and described. The plots of χ_MT versus T of the complex showed that the χ_MT values, after visible light illumination, were enhanced by about 25% as compared to before irradiation in the temperature range of 5-40 K.     

Luminescence of NaGdFPO4:Ln after VUV excitation: A comparison with GdPO4:Ln (Ln=Ce, Tb)

The phosphors NaGdFPO₄:Ln³⁺ and GdPO₄:Ln³⁺ (for Ln³⁺=Ce³⁺ and Tb³⁺) were prepared by solid-state reaction technique, the VUV-vis spectroscopic properties of the phosphors were investigated, and we vividly compare the luminescence of Ce³⁺ and Tb³⁺ in the hosts. For phosphors GdPO₄:Ln³⁺, the band near 155 nm in VUV excitation spectrum is assumed to be the host-related absorption, and for NaGdFPO₄:Ln³⁺ the absorption is moved to longer wavelength, near 170 nm, showing the P-O bond covalency increased after fluoridation. The f-d transitions of Ce³⁺ and Tb³⁺ in the host lattices are assigned and corroborated, and it was found that the 5d states are with lower energy in NaGdFPO₄:Ln³⁺ than those in GdPO₄:Ln³⁺. For fluoridation of GdPO₄:Ln³⁺ to NaGdFPO₄:Ln³⁺, the energy change of Ln³⁺ (Ln=Ce, Tb) 5d states is consistent with that of host-related absorption.     

Electronic and mechanical properties of 5d transition metal mononitrides via first principles

The electronic and mechanical properties of 5d transition metal mononitrides from LaN to AuN are systematically investigated by use of the density-functional theory. For each nitride, six structures are considered, i.e., rocksalt, zinc blende, CsCl, wurtzite, NiAs and WC structures. Among the considered structures, rocksalt structure is the most stable for LaN, HfN and AuN, WC structure for TaN, NiAs structure for WN, wurtzite structure for ReN, OsN, IrN and PtN. The most stable structure for each nitride is mechanically stable. The formation enthalpy increases from LaN to AuN. For LaN, HfN and TaN, the formation enthalpy is negative for all the considered structures, while from WN to AuN, except wurtzite structure in ReN, the formation enthalpy is positive. The calculated density of states shows that they are all metallic. ReN in NiAs structure has the largest bulk modulus, 418 GPa. The largest shear modulus 261 GPa is from TaN in WC structure. Trends are discussed.     

First observation of intra-5f fluorescence from an actinyl center: Np(VI) near-IR emission in Cs2U(Np)O2Cl4

Fluorescence from an excited 5f state of Np(VI) has been observed in the doped impurity system Cs₂U(Np)O₂Cl₄. This is the first intra-5f fluorescence transition that has been detected at room temperature in a condensed-phase system with an actinyl (An(VI)O₂²⁺) core, and it is a rare example of fluorescence of any kind from non-uranyl ions of this type. The emission originates from an excited state approximately 6890 cm⁻¹ above the ground state. Its emission spectrum and fluorescence lifetime at 295 K will be discussed. Vibronic structure in the emission spectrum is assigned based on comparison with the detailed analysis of the absorption spectra published by Denning et al.     

[H2en]2{La2M(SO4)6(H2O)2} (M=Co, Ni): First organically templated 3d-4f mixed metal sulfates

The first organically templated 3d-4f mixed metal sulfates, [H₂en]₂{La₂M(SO₄)₆(H₂O)₂} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediamine cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions).     

5-Cyanoacetylpyrimidines as intermediates for 7-aryl-6-cyanopyrido[2,3-d]pyrimidin-5-ones

The reactions of N⁴- and 5-cyanoacetyl derivates of 4-aminopyrimidines with aromatic aldehydes have yielded the N-(pyrimidin-4-yl)-3-arylacrylamides and the dihydropyrido[2,3-d]pyrimidines, respectively. The first reaction was a Claisen-Schmidt reaction catalyzed by base, and the second one proceeded via thermal cyclocondensation.     

Tri-component reaction of 2-alkyl-4,5-dichloropyridazin-3(2H)-ones: synthesis of 5-cyano-5-(pyrimidin-2-yl)-2,7-dialkyl-5H-dipyridazino-[4,5-b:4,5-e]-4H-thiopyran-1,6-dione and 2-(4-cyanophenoxy) pyrimidine

Reaction of 2-alkyl-4,5-dichloropyridazin-3(2H)-ones with p-cyanophenol and 2-mercaptopyrimidine in the presence of base gave 2,4,5-trisubstituted-pyridazin-3(2H)-ones 4-9, 2-(4-cyanophenoxy)pyrimidine (10) and 5-cyano-5-(pyrimidin-2-yl)-2,7-dialkyl-5H-dipyridazino[4,5-b:4,5-e]-4H-thiopyran-1,6-diones 11 as a novel heterocycle.     

A new method for pyrrole peri-annulation: synthesis of 1H-1,5,7-triazacyclopenta[c,d]phenalenes from 1H-perimidines

New methods for the synthesis of 1H-1,5,7-triazacyclopenta[c,d]phenalenes have been developed based on a sequence involving Schmidt reaction of keto-perimidines and acylation of the intermediate amides with 1,3,5-triazines or carboxylic acids. The same synthetic sequence starting from the corresponding alkylperimidine includes acylation with acetic acid as the first step.     

Synthesis and properties of novel 5-(cyclohepta-2′,4′,6′-trienylidene)pyrimidine-2(1H),4(3H),6(5H)-triones: methodology for synthesizing cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborates

Novel condensation reaction of tropone with N-substituted and N,N′-disubstitued barbituric acids in Ac₂O afforded 5-(cyclohepta-2′,4′,6′-trienylidene)pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (8a-f) in moderate to good yields. The ¹³C NMR spectral study of 8a-f revealed that the contribution of zwitterionic resonance structures is less important as compared with that of 8,8-dicyanoheptafulvene. The rotational barriers (ΔG^‡) around the exocyclic double bond of mono-substituted derivatives 8a-c were obtained to be 14.51-15.03 kcal mol⁻¹ by the variable temperature ¹H NMR measurements. The electrochemical properties of 8a-f were also studied by CV measurement. Upon treatment with DDQ, 8a-c underwent oxidative cyclization to give two products, 7 and 9-substituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborates (11a-c·BF₄⁻ and 12a-c·BF₄⁻) in various ratios, while that of disubstituted derivatives 8d-f afforded 7,9-disubstituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (11d-f·BF₄⁻) in good yields. Similarly, preparation of known 5-(1′-oxocycloheptatrien-2′-yl)-pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (14a-d) and novel derivatives 14e,f was carried out. Treatment of 14a-c with aq. HBF₄/Ac₂O afforded two kinds of novel products 11a-c·BF₄⁻ and 12a,c·BF₄⁻ in various ratios, respectively, while that of 14d-f afforded 11d-f. The product ratios of 11a-c·BF₄⁻ and 12a-c·BF₄⁻ observed in two kinds of cyclization reactions were rationalized on the basis of MO calculations of model compounds 20a and 21a. The spectroscopic and electrochemical properties of 11a-f·BF₄⁻ and 12a-c·BF₄⁻ were studied, and structural characterization of 11c·BF₄⁻ based on the X-ray crystal analysis and MO calculation was also performed.     

Photoluminescent behavior of SrB4O7:RE (RE=Sm and Eu) prepared by Pechini, combustion and ceramic methods

This work reports the preparation of system containing RE²⁺ ions (RE=Sm and Eu)-doped in SrB₄O₇ matrix by ceramic, Pechini and combustion methods. These compounds were prepared by reduction of RE³⁺ to RE²⁺ in air, which exhibit some different features according to the preparation method. Photoluminescent properties of these systems were investigated based on the emission and excitation spectral data. The emission spectra of SrB₄O₇:Eu²⁺ system prepared by combustion and Pechini methods are characterized by a broad band assigned to interconfigurational 4f⁶5d→4f⁷ transition, while SrB₄O₇:Sm²⁺ compound exhibit narrow emission bands arising from intraconfigurational-4f⁶ also shows ⁴G_5/2→⁶H_J′ transitions ( and ) arising from Sm³⁺ ion, transitions. SrB₄O₇:RE system prepared by combustion method presents emission bands from RE³⁺ ions as intense as that arising from RE²⁺, suggesting that the preparation route is not efficient for the reduction RE³⁺→RE²⁺ process. Emission quantum efficiency and radiative emission rates of Sm²⁺ ion are determined and discussed.     

InCl3 and ZrCl4 catalyzed regioselective reaction of 2,2′-dihydroxybiphenyl with terminal alkynes: synthesis of new dibenzo[d,f][1,3]dioxepines

The regioselective reaction of 2,2′-dihydroxybiphenyl with terminal alkynes was found to be rapidly catalyzed by InCl₃ and ZrCl₄. The chemoselectivity of catalysts and alkynes for biphenol over water, together with the reaction mechanism are discussed in details.     

Indium(III) chloride catalyzed one step synthesis of some new dibenzo(d,f)(1,3)dioxepines and 12H-dibenzo(d,g)(1,3)dioxocin derivatives

In the presence of catalytic amount of indium(III) chloride (10 mol %), 2,2′-dihydroxybiphenyl and bis(2-hydroxyphenyl)methane react quickly, without using any solvent, with ketones or β-keto esters possessing at least one hydrogen atom in α to the ketone-carbonyl group, to afford some new dibenzo(d,f)(1,3)dioxepines and some 12H-dibenzo(d,g)(1,3)dioxocin derivatives, respectively.     

Synthesis of a 5-alkoxypyrido[4,3-d]pyrimidin-4(3H)-one derivative via a regioselective Meisenheimer N-oxide rearrangement

The synthetic strategy towards a 5-alkoxypyrido[4,3-d]pyrimidin-4(3H)-one is described utilizing a selective N-oxidation and subsequent regioselective Meisenheimer N-oxide rearrangement as key steps.     

The stereoselective synthesis of (E)-octafluoro-1,3,5-hexatriene and (3E,5E,7E)-dodecafluoro-1,3,5,7,9-decapentaene

(E)-(1,2-Difluoro-1,2-ethenediyl)bis[tributylstannane], 3, readily undergoes a Pd(PPh₃)₄/CuI-catalyzed cross-coupling reaction with iodotrifluoroethene to yield (E)-octafluoro-1,3,5-hexatriene, 4, in high isomeric purity. (1Z,3E,5Z)-(1,2,3,4,5,6-Hexafluoro-1,3,5-hexenetriyl)bis[tributylstannane], 7, was sequentially prepared from (1Z,3E,5Z)-(1,2,3,4,5,6-hexafluoro-1,3,5-hexenetriyl)bis[triethylsilane], 5, which was prepared via a Pd(PPh₃)₄/CuI-catalyzed cross-coupling reaction of 3 with (E)-1,2-difluoro-1-iodo-2-triethylsilylethene, 6. Pd(PPh₃)₄/CuI cross-coupling of 7 with iodotrifluoroethene gave (3E,5E,7E)-dodecafluoro-1,3,5,7,9-decapentaene, 8.     

A convenient synthesis of 5-arylamino-4H-pyran-4-ones using palladium-catalyzed amination

A concise approach to 5-arylamino-4H-pyran-4-ones is described via palladium-catalyzed amination reaction. The methodology involved in this Letter is based on protection/deprotection protocols and on manipulation of the 5-hydroxy group of readily available kojic acid. It would provide a new entry to a range of 5-arylamino-4H-pyran-4-ones via Buchwald-Hartwig-type amination reaction on 4H-pyran-4-one unit.     

Synthesis and reactions of 5-tributylstannyl-4-fluoro-1H-pyrazole

The palladium-catalyzed cross-coupling reactions of 5-tributylstannyl-4-fluoro-1H-pyrazole with aryl iodides provided high yields of the corresponding 5-aryl-4-fluoro-1H-pyrazoles. Furthermore, these cross-coupling reactions proceeded smoothly under an atmosphere of carbon monoxide (CO) to afford the corresponding 5-acyl-4-fluoro-1H-pyrazoles as CO-insertion products.     

Synthesis of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one

Derivatives of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one were prepared in four steps starting from substituted benzonitriles bearing a functionalized amino group in the adjacent position. The unsubstituted- and the dimethoxy-pyrrolizinoindolones 5a and 5b exhibited modest activity against the HL-60(TB) human leukemia cell line, whereas the N-methylated dimethoxy-pyrrolizinoindolone 6b showed to be selective against MOLT-4 leukemia, A549/ATCC, HOP-92, and NCI-H460 non-small cell lung cancer, and CAKI-1 renal cancer cell lines.     

Effects of partial anion substitution on the thermoelectric properties of silver(I) chalcogenide halides in the system Ag5Q2X with Q=Te, Se and S and X=Br and Cl

A selection of mixed conducting silver chalcogenide halides of the general formula Ag₅Q₂X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag₅Te₂Cl showed a defined d¹⁰-d¹⁰ interaction in the disordered cation substructure at elevated temperatures where Ag₅Te₂Cl is present in its high temperature α-phase. A significant drop of the thermal diffusivity has been observed during the β−α phase transition reducing the values from 0.12 close to 0.08 mm² s⁻¹. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values.Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag₅Q₂X were determined around the silver-order/disorder β−α phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the β−α phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m⁻¹ K⁻¹ at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag₅Q₂X phases.     

Efficient palladium-mediated or base-induced 5-endo-dig cyclisation of C5-alkynylated pyrimidine derivatives: conventional and microwave-assisted synthesis of novel furo[2,3-d]pyrimidines

A series of the novel 5-alkynyl- and furo[2,3-d]pyrimidine derivatives in which the sugar moiety is replaced by a methoxymethyl (MOM) group is synthesised using the Sonogashira cross-coupling reaction under both conventional and microwave conditions, in good to excellent yields. The 5-endo-dig cyclisation of 5-alkynylpyrimidine derivatives promoted by a Pd-catalyst or base gives the corresponding furo[2,3-d]pyrimidines in good yields.     

Convenient synthesis of 5-methylene-4-substituted-2(5H)-furanones

A synthesis of novel 4-(substituted)benzyl-5-methylene-2(5H)-furanones involving Stobbe condensation of substituted aldehydes with ethyl levulinate followed by treatment with acetic anhydride in the presence of sodium acetate, has been developed.