Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U-Furoate Phase Formation

Uranium(IV) complexation by 2-furoic acid (2-FA) was examined to better understand the effects of ligand identity and reaction conditions on species formation and stability. Five compounds were isolated: [UCl₂(2-FA)₂(H₂O)₂]_n ( 1 ), [U₄Cl₁₀O₂(THF)₆(2-FA)₂] ⋅ 2 THF ( 2 ), [U₆O₄(OH)₄(H₂O)₃(2-FA)₁₂] ⋅ 7 THF ⋅ H₂O ( 3 ), [U₆O₄(OH)₄(H₂O)₂(2-FA)₁₂] ⋅ 8.76 H₂O ( 4 ), and [U₃₈Cl₄₂O₅₄(OH)₂(H₂O)₂₀] ⋅ m H₂O ⋅ n THF ( 5 ). The structures were determined by single-crystal X-ray diffraction and further characterized by Raman, IR, and optical absorption spectroscopy. The thermal stability and magnetic behavior of the compounds were also examined. Variations in the synthetic conditions led to notable differences in the structural units observed in the solid state. At low H₂O/THF ratios, a tetranuclear oxo-bridged [U₄O₂] core was isolated. Aging of this solution resulted in the formation a U₃₈ oxo cluster capped by chloro and water ligands. However, at increasing water concentrations only hexanuclear units were observed. In all cases, at temperatures of 100–120 °C, UO₂ nanoparticles formed.     

Donor-Stabilised [SbF4]+: SbF5 as a Fluoride-Ion Donor

Antimony pentafluoride is a strong Lewis acid and fluoride-ion acceptor that has not previously demonstrated any discreet fluoride-ion donor properties. The first donor-stabilised [SbF₄]⁺ cations were prepared from the autoionisation of SbF₅ in the presence of bidentate N-donor ligands 2,2’-bipyridine (bipy) and 1,10-phenanthroline (phen) as their [SbF₆]⁻ salts. The [SbF₄(N−N)][Sb₂F₁₁] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF₅⋅SO₂ to [SbF₄(N−N)][SbF₆] in liquid SO_2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF₄(phen)][SbF₆] ⋅ 3CH₃CN and [SbF₄(phen)][SbF₆] ⋅ 2SO₂ were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron-pair donation from N to Sb stabilizes [SbF₄]⁺ with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand-centred.     

In Situ Metal-Assisted Ligand Modification Induces Mn4 Cluster-to-Cluster Transformation: A Crystallography,Mass Spectrometry,and DFT Study

Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H₄L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H₃L′) was found to be metal-assisted, occurs under solvothermal conditions (H₂O/CH₃OH), and leads to [Mn^II₄(H₃L)₄Cl₂]Cl₂ ⋅ 5 H₂O ⋅ 5 CH₃OH ( Mn₄L₄ ) and [Mn^II₄(H₂L′)₆(μ₃-OH)]Cl ⋅ 4 CH₃OH ⋅ H₂O ( Mn₄L′₆ ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn₄L₄ from the reactants via [MnL] and [Mn₂L₂] below 80 °C, and then disassembly to [MnL] and [MnL₂] followed by ligand modification before reassembly to Mn₄L′₆ via [MnL′], [MnL′₂], and [Mn₂L′₃] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn₄L_xL′_6−x] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during “black-box” reactions.     

Proton mobility in complex [RhL4Cl2]HSO4 · nH2SO4 · mH2O salts (L = Py, γ-picoline)

The method of deposition from solutions was used to synthesize [RhL ₄Cl₂]HSO₄ · nH₂SO₄ · mH₂O complex salts (L = Py, γ-picoline), n ≈ 0.5−0.6, m ≈ 5−6. According to the data of X-ray phase analysis, the crystal structure of these salts is formed by layers of cations separated by layers consisting of anions molecules of sulfuric acid and water connected through a system of hydrogen bonds. Calorimetric methods were used to study phase transitions and the range of thermal stability of salts. The method of ¹H NMR spectroscopy discovered that protons within the {HSO₄⁻ · nH₂SO₄ · mH₂O} subsystem featured enhanced conductivity. Conductivity studies showed that trans-[RhL ₄Cl₂]HSO₄ · nH₂SO₄ · mH₂O samples had high proton conductivity.     

Zur Kenntnis der Sulfito-kobalt(III)-Ammine. III. Hydrogensulfitokobalt(III)-Ammine

Sulphito Cobalt(III) Ammines. III. Hydrogensulphito Cobalt(III) Ammines Concentrated acids react with [CoSO₃(NH₃)₅]⁺ salts hydrogen- sulphitopentaamminecobalt(III) complexes. [Co(HSO₃)(NH₃)₅]Cl₂, [Co(HSO₃)(NH₃)₅]Br₂ and [Co(HSO₃)(NH₃)₅](HSO₄)₂·H₂O have been isolated. These substances are yellow coloured in contrast to an earlier work which reported red colour. Furthermore, the hydrogensulphitoacidotetreaammine complexes [Co(HSO₃)Cl(NH₃)₄]Cl, [Co(HSO₃)Cl(NH₃)₄]ClO₄·H₂O, [Co(HSO₃)Br(NH₃)₄]Br and [Co(HSO₃) CN(NH₃)₄]Cl habe been prepared. [Co(HSO₃)Br(NH₃)₄]Br is losing spontaneously HBr forming [CoSO₃Br(NH₃)₄]. The neutral complex [Co(HSO₃)SO₃(NH₃)₄]·1/2H₂O has been obtained from cis- NH₄[Co(SO₃)₂(NH₃)₄] and HCl. The absorption spectra in the IR, visible and UV region are reported and discussed. The HSO₃ group is coordinated to Co through the S atom. The Co? S bond is weaker than in the sulphito complexes as concluded from the RAMAN spectrum. In the new complexes, the hydrogensulphito ligand causes a minor trans effect than the sulphito ligand.     

Structural Transformations and Spin-Crossover in [FeL2]2+ Salts (L=4-{tert-Butylsulfanyl}-2,6-di{pyrazol-1-yl}pyridine): The Influence of Bulky Ligand Substituents

4-(tert-Butylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine (L) was obtained in low yield from a one-pot reaction of 2,4,6-trifluoropyridine with 2-methylpropane-2-thiolate and sodium pyrazolate in a 1:1:2 ratio. The materials [FeL₂][BF₄]₂⋅solv ( 1[BF₄]₂ ⋅solv) and [FeL₂][ClO₄]₂⋅solv ( 1[ClO₄]₂ ⋅solv; solv=MeNO₂, MeCN or Me₂CO) exhibit a variety of structures and spin-state behaviors including thermal spin-crossover (SCO). Solvent loss on heating 1[BF₄]₂ ⋅x MeNO₂ (x≈2.3) occurs in two steps. The intermediate phase exhibits hysteretic SCO around 250 K, involving a “reverse-SCO” step in its warming cycle at a scan rate of 5 K min⁻¹. The reverse-SCO is not observed in a slower 1 K min⁻¹ measurement, however, confirming its kinetic nature. The final product [FeL₂][BF₄]₂⋅0.75 MeNO₂ was crystallographically characterized, and shows abrupt but incomplete SCO at 172 K which correlates with disorder of an L ligand. The asymmetric unit of 1[BF₄]₂ ⋅y Me₂CO (y≈1.6) contains five unique complex molecules, four of which undergo gradual SCO in at least two discrete steps. Low-spin 1[ClO₄]₂ ⋅0.5 Me₂CO is not isostructural with its BF₄⁻ congener, and undergoes single-crystal-to-single-crystal solvent loss with a tripling of the crystallographic unit cell volume, while retaining the P space group. Three other solvate salts undergo gradual thermal SCO. Two of these are isomorphous at room temperature, but transform to different low-temperature phases when the materials are fully low-spin.     

Reliable Functionalization of 5,6-Fused Bicyclic N-Heterocycles Pyrazolopyrimidines and Imidazopyridazines via Zinc and Magnesium Organometallics

DFT-calculations allow prediction of the reactivity of uncommon N-heterocyclic scaffolds of pyrazolo[1,5-a]pyrimidines and imidazo[1,2-b]pyridazines and considerably facilitate their functionalization. The derivatization of these N-heterocycles was realized using Grignard reagents for nucleophilic additions to 5-chloropyrazolo[1,5-a]pyrimidines and TMP₂Zn ⋅ 2 MgCl₂ ⋅ 2 LiCl allowed regioselective zincations. In the case of 6-chloroimidazo[1,2-b]pyridazine, bases such as TMP₂Zn ⋅ MgCl₂ ⋅ 2 LiCl, in the presence or absence of BF₃ ⋅ OEt₂, led to regioselective metalations at positions 3 or 8. Subsequent functionalizations were achieved with TMPMgCl ⋅ LiCl, producing various polysubstituted derivatives (up to penta-substitution). X-ray analysis confirmed the regioselectivity for key functional heterocycles.     

Effect of Axial Ligands on Easy-Axis Anisotropy and Field-Induced Slow Magnetic Relaxation in Heptacoordinated FeII Complexes

A rational approach to modulating easy-axis magnetic anisotropy by varying the axial donor ligand in heptacoordinated Fe^II complexes has been explored. In this series of complexes with formulae of [Fe(H₄L)(NCS)₂] ⋅ 3 DMF ⋅ 0.5 H₂O ( 1 ), [Fe(H₄L)(NCSe)₂] ⋅ 3 DMF ⋅ 0.5 H₂O ( 2 ), and [Fe(H₄L)(NCNCN)₂] ⋅ DMF ⋅ H₂O ( 3 ) [H₄L=2,2′-{pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)}bis(N-phenylhydrazinecarboxamide)], the axial positions are successively occupied by different nitrogen-based π-donor ligands. Detailed dc and ac magnetic susceptibility measurements reveal the existence of easy-axis magnetic anisotropy for all of the complexes, with 1 [U_eff=21 K, τ₀=1.72×10⁻⁶ s] and 2 [U_eff=25 K, τ₀=2.25×10⁻⁶ s] showing field-induced slow magnetic relaxation behavior. However, both experimental studies and theoretical calculations indicate the magnitude of the D value of complex 3 to be larger than those of complexes 1 and 2 due to the axial bond angle being smaller than that for an ideal geometry. Detailed analysis of the field and temperature dependences of relaxation time for 1 and 2 has revealed that multiple relaxation processes (quantum tunneling of magnetization, direct, and Raman) are involved in slow magnetic relaxation for both of these complexes. Magnetic dilution experiments support the role of intermolecular short contacts.     

A Series of Polyoxometalate-Viologen Photochromic Materials for UV Probing,Amine Detecting and Inkless and Erasable Printing

In this work, by using two kinds of viologen ligands three POM-based Compounds were obtained under hydrothermal conditions, namely [Ag^I(bmypd)_0.5(β-Mo₈O₂₆)_0.5] (1) (bmypd ⋅ 2Cl=1,1′-[Biphenyl-4,4′-bis(methylene)]bis(4,4′-bipyridyinium)dichloride), [Ag^I₂(bypy)₄(HSiW₁₂O₄₀)₂] ⋅ 14H₂O (2) and [Ag^I(bypy)(γ-Mo₈O₂₆)_0.5] (3) (bypy⋅Cl=1-Benzyl-4,4′-bipyridyinium chloride). The structures were characterized by Fourier transform infrared spectroscopy (FT–IR), Powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction. Compounds 1–3 show excellent photochromic ability with fast photoresponse under the irradiation of ultraviolet light with different degrees of color changes. So compounds 1–3 can be used as visible ultraviolet detectors. Compounds 1–3 also possess photoluminescence properties with fast and excellent fluorescence quenching effect. Compounds 1–3 also can be used as inkless and erasable printing materials with suspensions of 1–3 applied to filter paper. Compounds 1–3 can also produce color changes in amine vapor environment, especially in an NH₃ atmosphere. Compounds 1–3 can be used as organic amine detectors.     

Syntheses,Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4 (Ng=Kr,Xe), and (CrOF4)∞

The noble-gas difluoride adducts, NgF₂ ⋅ CrOF₄ and NgF₂ ⋅ 2CrOF₄ (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single-crystal X-ray diffraction. The low fluoride ion affinity of CrOF₄ renders it incapable of inducing fluoride ion transfer from NgF₂ (Ng=Kr and Xe) to form ion-paired salts of the [NgF]⁺ cations having either the [CrOF₅]⁻ or [Cr₂O₂F₉]⁻ anions. The crystal structures show the NgF₂ ⋅ CrOF₄ adducts are comprised of F_t−Ng−F_b- - -Cr(O)F₄ structural units in which NgF₂ is weakly coordinated to CrOF₄ by means of a fluorine bridge, F_b, in which Ng−F_b is elongated relative to the terminal Ng−F_t bond. In contrast with XeF₂ ⋅ 2MOF₄ (M=Mo or W) and KrF₂ ⋅ 2MoOF₄, in which the Lewis acidic, F₄(O)M- - -F_b- - -M(O)F₃ moiety coordinates to Ng through a single M- - -F_b−Ng bridge, both fluorine ligands of NgF₂ coordinate to CrOF₄ molecules to form F₄(O)Cr- - -F_b−Ng−F_b- - -Cr(O)F₄ adducts in which both Ng−F_b bonds are only marginally elongated relative to the Ng−F bonds of free NgF₂. Quantum-chemical calculations show that the Cr−F_b bonds of NgF₂ ⋅ CrOF₄ and NgF₂ ⋅ 2CrOF₄ are predominantly electrostatic with a small degree of covalent character that accounts for their nonlinear Cr- - -F_b−Ng bridge angles and staggered O−Cr- - -F_b−Ng−F_t dihedral angles. The crystal structures and Raman spectra of two CrOF₄ polymorphs have also been obtained. Both are comprised of fluorine-bridged chains that are cis- and trans-fluorine-bridged with respect to oxygen.     

Synthesis and properties of polynitrosyl molybdenum complexes

Summary The reaction of [Mo(CO)₆] with NOHSO₄ gives new [Mo(NO)₂(CO)₂(HSO₄)₂], [Mo(NO)₃(HSO₄)₃] and [Mo(NO)₄(HSO₄)₂] (HSO₄)₂ polynitrosyl molybdenum complexes. The structure of none of the complexes was fully determined. The last is probably a hyponitritonitrosyl complex. [Mo(NO)₃(HSO₄)₃] and [Mo(NO)₄(HSO₄)₂] (HSO₄)₂ with EtAlCl₂ form heterogeneous catalytic systems for olefin metathesis.     

Sunlight-Induced In Situ Isomerization of Both Ligands in a Mixed-Ligand Coordination Polymer: From Photosalient to Photoinert Crystals

Reaction of Zn(NO₃)₂ ⋅ 6H₂O, maleic acid (H₂mal) and trans-4-(1-naphthylvinyl)pyridine (trans-nvp) in the dark results in the formation of a one-dimensional coordination polymer (1D CP) [Zn(mal)(trans-nvp)] ( 1 ), which is photosalient in nature. The crystals of 1 pop violently under UV light and moderately in sunlight, and generate cyclobutane ligands. However, the same reaction mixture kept in visible light exhibits the rare example of in situ isomerization of both ligands: cis-trans transformation of maleate and trans-cis isomerization of the nvp ligands, and subsequent formation of another 1D CP [Zn(fum)(cis-nvp)₂(H₂O)₂] ( 2 , H₂fum=fumaric acid), which is found to be photoinert. Thus, altering the reaction condition from dark to visible light gives rise to photosalient to photoinert crystals.     

Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands

This contribution focuses on complex [Mo₂(H)₂(μ-Ad^Dipp2)₂] ( 1 ) and tetrahydrofuran and pyridine adducts [Mo₂(H)₂(μ-Ad^Dipp2)₂(L)₂] ( 1⋅thf and 1⋅py ), which contain a trans-(H)Mo≣Mo(H) core (Ad^Dipp2=HC(NDipp₂)₂; Dipp=2,6-iPr₂C₆H₃). Computational studies provide insights into the coordination and electronic characteristics of the central trans-Mo₂H₂ unit of 1 , with four-coordinate, fourteen-electron Mo atoms and ϵ-agostic interactions with Dipp methyl groups. Small size C- and N-donors give rise to related complexes 1⋅L but only one molecule of P-donors, for example, PMe₃, can bind to 1 , causing one of the hydrides to form a three-centered, two-electron (3c-2e) Mo-H→Mo bond ( 2⋅PMe₃ ). A DFT analysis of the terminal and bridging hydride coordination to the Mo≣Mo bond is also reported, along with reactivity studies of the Mo−H bonds of these complexes. Reactions investigated include oxidation of 1⋅thf by silver triflimidate, AgNTf₂, to afford a monohydride [Mo₂(μ-H)(μ-NTf₂)(μ-Ad^Dipp2)₂] ( 4 ), with an O,O’-bridging triflimidate ligand.     

Unraveling the Mechanisms of the Excited-State Intermolecular Proton Transfer (ESPT) for a D-π-A Molecular Architecture

Precise revealing the mechanisms of excited-state intermolecular proton transfer (ESPT) and the corresponding geometrical relaxation upon photoexcitation and photoionization remains a formidable challenge. In this work, the compound (E)-4-(((4H-1,2,4-triazol-4-yl)imino)methyl)-2,6-dimethoxyphenol (TIMDP) adopting a D-π-A molecular architecture featuring a significant intramolecular charge transfer (ICT) effect has been designed. With the presence of perchloric acid (35 %), TIMDP can be dissolved through the formation of a HClO₄–H₂O–OH(TIMDP)–N(TIMDP) hydrogen-bonding bridge. At the ground state, the ICT effect is dominant, giving birth to crystals of TIMDP. Upon external stimuli (e.g., UV light irradiation, electro field), the excited state is achieved, which weakens the ICT effect, and significantly promotes the ESPT effect along the hydrogen-bonding bridge, resulting in crystals of [HTIMDP]⁺ ⋅ [H₂O] ⋅ [ClO₄]⁻. As a consequence, the mechanisms of the ESPT can be investigated, which distorted the D-π-A molecular architecture, tuned the emission color with the largest Stokes shift of 242 nm, and finally, high photoluminescence quantum yields (12 %) and long fluorescence lifetimes (8.6 μs) have achieved. These results not only provide new insight into ESPT mechanisms, but also open a new avenue for the design of efficient ESPT emitters.     

Dendritic Iron Porphyrins with a Tethered Axial Ligand as New Model Compounds for Heme Monooxygenases

The novel iron(III) porphyrin dendrimers of generation zero ([ 1 ⋅Fe^III]Cl), one ([ 2 ⋅Fe^III]Cl), and two ([ 3 ⋅Fe^III]Cl) (Fig. 1) were prepared (Schemes 1 and 3) as models of heme monooxygenases. They feature controlled axial ligation at the Fe center by one imidazole tethered to the porphyrin core and possess a vacant coordination site available for ligand binding and catalysis. The high purity of the dendrimers and the absence of structural defects was demonstrated by matrix‐assisted laser‐desorption‐ionization time‐of‐flight (MALDI‐TOF) mass spectrometry (Fig. 3). The electronic properties of the Fe^III porphyrin dendrimers and comparison compounds [ 4 ⋅Fe^III]Cl and [ 12 ⋅Fe^III(1,2‐Me₂Im)]Cl (1,2‐Me₂Im=1,2‐dimethylimidazole) were investigated by UV/VIS and EPR (electronic paramagnetic resonance) spectroscopy, as well as by measurements of the magnetic moments by the Evans‐Scheffold method. Epoxidation of olefins and oxidation of sulfides to sulfoxides, catalyzed by the new dendritic metalloporphyrins, were investigated in CH₂Cl₂ with iodosylbenzene as the oxidant (Tables 1 and 2). The total turnover numbers were found to increase with the size of the dendrimer, due to improved catalyst stability at higher dendritic generations (Figs. 4 and 5). The second‐generation complex [ 3 ⋅Fe^III]Cl was, therefore, the most efficient catalyst in the series, despite the fact that its active site is considerably hindered by the encapsulation inside the sterically demanding, fluctuating dendritic wedges. Very high product selectivities were observed in all oxidation reactions, regardless of dendrimer generation.     

A Domino Fusion of an Organic Ligand Depended on Metal-Induced and Oxygen Insertion,Unraveled by Crystallography,Mass Spectrometry,and DFT Calculations

Herein, the reaction of (1-methyl-1 H-benzo[d]imidazol-2-yl)methanamine ( L1 ) with Co(H₂O)₆Cl₂, in CH₃CN at 120 °C, leading to the 2,3,5,6-tetrakis(1-methyl-1 H-benzo[d]imidazol-2-yl)pyrazine ( 3 ), isolated as a dimeric cluster {[Co^II₂( 3 )Cl₄] ⋅ 2 CH₃CN} ( 2 ), is reported. When O₂ and H₂O are present, (1-methyl-1 H-benzo[d]imidazole-2-carbonyl)amide (H L1′ ) is first formed and crystallized as [Co^III( L1 )₂( L1′ )]Cl₂ ⋅ 2 H₂O ( 4 ) before fusion of H L1′ with L1 , giving 1-methyl-N-(1-methyl-1 H-benzo[d]imidazol-2-carbonyl)-1 H-benzo[d]imidazol-2-carboxamide (H L2′′ ) forming a one-dimensional (1D) chain of [Co^II₃( L2′′ )₂Cl₄]_n ( 5 ). The combination of crystallography and mass spectrometry (ESI-MS) of isolated crystals and the solutions taken from the reaction as a function time reveal seven intermediate steps leading to 2 , but six steps for 5 , for which a different sequence takes place. Control and isotope labeling experiments confirm the two carbonyl oxygen atoms in 5 originate from both air and water. The dependence on the metals, compared with FeCl₃ ⋅ 6 H₂O leading to a stable triheteroarylmethyl radical, is quite astounding, which could be attributed to the different oxidation states of the metals and coordination modes confirmed by DFT calculations. This metal and valence dependent process is a very useful way for selectively obtaining these large molecules, which are unachievable by common organic synthesis.     

Nine-coordinated Eu3+ Dipicolinate Compounds: Different Crystal Structures and Luminescence Properties as a Function of pH

Two compounds, Na₃[Eu(DPA)₃] ⋅ 14H₂O and [Eu(DPA)(HDPA)(H₂O)₂] ⋅ 4H₂O, were created and the structure determined using single crystal X-ray diffraction. The single crystal luminescence properties were compared and related to the Eu³⁺ coordination geometry. The formation of single crystals from solutions of Eu(CF₃SO₃)₃ and H₂DPA was found change with the pH value of the H₂DPA solution. Mixtures of Na₃[Eu(DPA)₃] ⋅ 14H₂O and [Eu(DPA)(HDPA)(H₂O)₂] ⋅ 4H₂O were observed with a pH ratio between the two structures. While visual inspection showed that all samples contained both Na₃[Eu(DPA)₃] ⋅ 14H₂O and [Eu(DPA)(HDPA)(H₂O)₂] ⋅ 4H₂O, the PXRD and luminescence data did not immediately reveal that the samples were pure. Having discovered that the samples were indeed mixtures, quantification was attempted by Rietveld refinement of the PXRD data, and the luminescence spectra were compared to those from single crystals. As the data was not found to reveal that the samples were mixtures, even though we knew that this was the case, we must urge caution when inferring structure-property relationships from powder samples. In this case we were able to isolate monophasic systems and do a comparative study, but this requires that the samples are identified as mixtures.     

Elucidating the Structural Chemistry of a Hysteretic Iron(II) Spin-Crossover Compound From its Copper(II) and Zinc(II) Congeners

Annealing [FeL₂][BF₄]₂ ⋅ 2 H₂O (L=2,6-bis-[5-methyl-1H-pyrazol-3-yl]pyridine) affords an anhydrous material, which undergoes a spin transition at T_1/2=205 K with a 65 K thermal hysteresis loop. This occurs through a sequence of phase changes, which were monitored by powder diffraction in an earlier study. [CuL₂][BF₄]₂ ⋅ 2 H₂O and [ZnL₂][BF₄]₂ ⋅ 2 H₂O are not perfectly isostructural but, unlike the iron compound, they undergo single-crystal-to-single-crystal dehydration upon annealing. All the annealed compounds initially adopt the same tetragonal phase but undergo a phase change near room temperature upon re-cooling. The low-temperature phase of [CuL₂][BF₄]₂ involves ordering of its Jahn–Teller distortion, to a monoclinic lattice with three unique cation sites. The zinc compound adopts a different, triclinic low-temperature phase with significant twisting of its coordination sphere, which unexpectedly becomes more pronounced as the crystal is cooled. Synchrotron powder diffraction data confirm that the structural changes in the anhydrous zinc complex are reproduced in the high-spin iron compound, before the onset of spin-crossover. This will contribute to the wide hysteresis in the spin transition of the iron complex. EPR spectra of copper-doped [Fe_0.97Cu_0.03L₂][BF₄]₂ imply its low-spin phase contains two distinct cation environments in a 2:1 ratio.     

Ionic Liquid Catalyzed One‐Pot Synthesis of 2H‐Pyridazino[1,2‐a]indazole‐1,6,9(11H)‐triones Via Three‐Component Reaction under Solvent‐Free Conditions

2H‐Pyridazino[1,2‐a]indazole‐1,6,9(11H)‐triones were synthesized through one‐pot, three‐component condesation of aldehydes, maleic hydrazide, and dimedone using a green and inexpensive Brönsted acidic ionic liquid 1‐methyl‐2‐pyrrolidinone hydrosulfate ([Hnmp]HSO₄) as catalyst under solvent‐free conditions. The method provided several advantages such as milder conditions, shorter reaction time, high yields, and environmentally benign procedure.     

Structural and Synthetic Insights into Sodium-Mediated-Ferration of Fluoroarenes

Exploiting chemical cooperation between Na and Fe(II) within the bimetallic base [dioxane ⋅ NaFe(HMDS)₃] ( I ), (dioxane=1,4-dioxane, HMDS=N(SiMe₃)₂) the selective ferration of fluorobenzene, 1-fluoronaphthalene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1-bromo-3,5-difluorobenzene, 3-fluoroanisole and 3,5-difluoroanisole has been realized, affording sodium ferrates [dioxane ⋅ Na(HMDS)(2-F-C₆H₄)Fe(HMDS)]_∞ ( 1 ), [dioxane ⋅ Na(HMDS)(2-F-C₁₀H₆)Fe(HMDS)]_∞ ( 2 ), [dioxane ⋅ {Na(HMDS)(2,5-F₂-C₆H₃)Fe(HMDS)}₂]_∞ ( 3 ), [dioxane ⋅ {Na(HMDS)(2,3,6-F₃-C₆H₂)Fe(HMDS)}₂]_∞ ( 4 ), [(dioxane)_1.5 ⋅ Na(HMDS)(2,4,6-F₃-C₆H₂)Fe(HMDS)]₂ ( 5 ), [(dioxane)_1.5 ⋅ {Na(HMDS)(4-Br-2,6-F₂-C₆H₂)Fe(HMDS)₂] ( 6 ), [{(dioxane)₂ ⋅ Na₂Fe(HMDS)₂(2-methoxy-6-F-C₆H₃)}⁺{Fe(HMDS)₃}⁻]_∞ ( 7 ) and [dioxane ⋅ {Na(HMDS)(4-methoxy-2,6-F₂-C₆H₂)Fe(HMDS)}₂]_∞ ( 8 ), respectively. Reactions take place under mild reaction conditions, with excellent control of the selectivity and no competing C−F bond activation is observed. Showcasing complex polymeric arrangements in some cases, the structures of compounds 1 – 8 have been determined by X-ray crystallographic studies. In all cases, the Fe(II) centers occupy the position in the relevant fluoroarene that was previously filled by a proton, confirming that these metallations are actually ferration processes whereas the Na atoms prefer to form Na⋅⋅⋅F dative interactions. Compounds 1 – 8 are thermally stable and do not undergo benzyne formation (through NaF elimination) and their formation contrasts with the inertness of Fe(HMDS)₂ which fails to act as a base to metallate fluoroarenes.