A whole school approach to literacy intervention

This research project reports on the process of developing a whole school approach to literacy intervention in one multi-ethnic, designated disadvantaged primary school. The study describes how teachers worked collaboratively, using items from a resource package Successful Intervention K-3 Literacy, to critically reflect on their pedagogy in their efforts to better address the needs of those students in their classes who appeared to have difficulties with literacy learning. A modified action research method was used by the teachers to devise a context-specific school plan. Within the plan, they allocated time and resources to assist them as they shared and developed their knowledge and skills to deal with the social, cultural, emotional, linguistic and cognitive needs of the identified students. As a result, the teachers developed individual literacy intervention programs for children experiencing difficulties. The programs included all the stake holders and were devised to be used in the mainstream classrooms. In addition, in order to facilitate consistency and continuity of approach from year to year for students experiencing difficulty with literacy learning, the teachers planned a system to store and pass on students\u27 records. Of particular interest were the actions taken to explore understandings about literacy interventions, the changes in teacher perceptions, and the use of individual literacy intervention programs for children experiencing difficulties with literacy learning. As a consequence of their involvement in the project, the teachers developed an integrated literacy intervention policy and a school plan to guide future strategies for literacy intervention

Variations of Structures and Phenoxazinone Synthase-like Activity of the Complexes Based on (Cu^II)₂Mn^II Node and Dicyanamide Spacer

Three new heterometallic Cu­(II)–Mn­(II) complexes, [{(CuL)₂Mn}₂­(μ_1,5-N­(CN)₂)­(CH₃CN)₂]­(ClO₄)₃ (<b>1</b>), [(CuL)₂Mn­(N­(CN)₂)₂]­·(H₂O) (<b>2</b>), and [(CuL)₂Mn­(μ_1,5-N­(CN)₂)₂]_<i>n</i> (<b>3</b>), have been synthesized using a Cu­(II)-metalloligand of an asymmetrically dicondensed Schiff base ligand (where H₂L = <i>N</i>-α-methylsalicylidene-<i>N</i>′-salicylidene-1,3-propanediamine). Complex <b>1</b> was formed when the ratio of [CuL]/Mn­(ClO₄)₂/NaN­(CN)₂ was 2:1:1, whereas complexes <b>2</b> and <b>3</b> were obtained with a 2:1:2 ratio of the same reactants on varying the reaction conditions. Single-crystal structural analyses reveal that complex <b>1</b> possesses a hexanuclear structure in which two (Cu^II)₂Mn^II units are connected by one μ_1,5-N­(CN)₂^– bridge, <b>2</b> is a discrete trinuclear species with two terminally coordinated N­(CN)₂^– ions to the Mn­(II), whereas complex <b>3</b> is a polymeric form of <b>2</b> with μ_1,5-N­(CN)₂^– bridges between Cu­(II) and Mn­(II) centers. The thermal variations of <i>dc</i> magnetic susceptibilities suggest that all three complexes (<b>1</b>–<b>3</b>) are antiferromagnetically coupled with comparable exchange coupling constants (−25.4, −22.8, and −22.0 cm^–1, respectively) which are expected from the Cu–O–Mn angles. All the complexes show biomemitic phenoxazinone synthase-like activity for the aerial oxidation of <i>o</i>-aminophenol to amino phenoxazinone. The turnover numbers (<i>k</i>_cat) for the process are 4966, 2021, and 1107 h^–1 for complexes <b>1</b>–<b>3</b> respectively. The mass spectral evidence on intermediates suggests that the cooperative activity of the two different metal ions, i.e., coordination of substrate to Mn­(II) and shuttling of oxidation state of Cu between I and II, is possibly operative in the oxidation process. The highest catalytic activity of <b>1</b> is attributed to the presence of one coordinating solvent molecule to Mn­(II)

Ni(II) Complex of N₂O₃ Donor Unsymmetrical Ligand and Its Use for the Synthesis of Ni^II–Mn^II Complexes of Diverse Nuclearity: Structures, Magnetic Properties, and Catalytic Oxidase Activities

A new mononuclear Ni­(II) complex [NiL] (<b>1</b>) of an unsymmetrically dicondensed N₂O₃ donor ligand, H₂L (<i>N</i>-α-methylsalicylidene-<i>N</i>′-3-methoxysalicylidene-1,3-propanediamine), has been synthesized. Complex <b>1</b> on reaction with Mn­(ClO₄)₂·6H₂O and NaN₃ in different molar ratios yielded three novel heterometallic Ni^II–Mn^II complexes, [(NiL)₂Mn­(N₃)]­(ClO₄) (<b>2</b>), [(NiL)₂Mn₂(N₃)₂(μ_1,1-N₃)₂(CH₃OH)₂] (<b>3</b>), and [{(NiL)₂Mn}₂(μ_1,3-N₃)­(H₂O)]·(CH₃OH),(ClO₄)₃ (<b>4</b>). The single crystal structure analyses show a trinuclear Ni^II₂Mn^II structure for complex <b>2</b> and a tetranuclear Ni^II₂Mn^II₂ structure where two dinuclear Ni^IIMn^II units are connected via μ_1,1-azido and phenoxido bridges for complex <b>3</b>. Complex <b>4</b> possesses a hexanuclear structure where two trinuclear Ni^II₂Mn^II units are connected via a μ_1,3-azido bridge. The temperature-dependent dc molar magnetic susceptibility measurements reveal that complexes <b>3</b> and <b>4</b> are antiferromagnetically coupled with the exchange coupling constants (<i>J</i>) of −4.97, −0.14, −0.55 cm^–1 for <b>3</b> and −3.94 cm^–1 for <b>4</b>. All complexes <b>2</b>–<b>4</b> show biomimetic catalytic oxidase activities. For catecholase like activity, the turnover numbers (<i>K</i>_cat) are 768, 1985, and 2309 h^<b>–</b>1 for complexes <b>2</b>–<b>4</b>, respectively, whereas for phenoxazinone synthase like activity, the turnover numbers are 3240, 3360, and 13 248 h^<b>–</b>1 for complexes <b>2</b>–<b>4</b>, respectively. This difference in catalytic efficiencies is attributed to the variations in structures of the complexes and formation of active Ni^II–Mn^II species in solution during catalysis. The mass spectral analyses suggest the probable intermediate formation and cyclic voltammetry measurement suggest the reduction of Ni­(II) to Ni­(I) during catalytic reaction. The very high catalytic efficiencies for aerial dioxygen activation of all these heterometallic complexes as well as the highest activity of <b>4</b> is attributed to the coordinatively unsaturated penta-coordinated geometry or hexa-coordinated geometry with a solvent water molecule around Mn­(II)

A wine red copper(II) complex of a tetradentate nitrogen donor showing two-electron oxidation. Generation of a copper(II)-phosphine bond

<p>Using the 1 : 2 condensate of benzil and 2-hydrazinopyridine as the ligand LH₂ (H: dissociable NH proton), the red complex Cu(LH₂)(ClO₄)₂ (<b>1</b>) was synthesized. The ligand also afforded the orange [Zn(LH₂)(OH₂)₂](ClO₄)₂ (<b>2</b>). The X-ray crystal structures of the ligand, <b>1</b> and <b>2</b> have been determined. The metals in <b>1</b> and <b>2</b> have octahedral N₄O₂ environments. <b>1</b> is paramagnetic with <i>μ</i>_eff of one unpaired electron (1.63 <i>μ</i>_B and displays an axial EPR spectrum in the solid state with <<i>g</i>> = 2.07, characteristic of a (d_x2_−y2)¹ ground state (<i>g</i>_|| > <i>g</i>_⊥; <i>A</i>_|| = 16 mT). In cyclic voltammetry, <b>1</b> displays a two-electron oxidation around 0.9 V <i>versus</i> NHE. The two-electron oxidized (coulometrically) solution of <b>1</b> (golden yellow) gives an EPR spectrum with <<i>g</i>> = 2.17 and <i>g</i>_|| < <i>g</i>_⊥. The reaction of PPh₃ with <b>1</b> yields the orange complex [Cu(LH₂)(PPh₃)](ClO₄)₂ (<b>4</b>). With the assumed chemical formula, the effective magnetization of <b>4</b> corresponds to one electron. Its EPR spectrum in the solid state is isotropic with <i>g</i> = 2.07. This <i>g</i> value yields a theoretical <i>μ</i>_eff of 1.80 <i>μ</i>_B at 298 K from Curie’s law, which matches very well with the experimental value of 1.89 <i>μ</i>_B at room temperature. Since single crystals of <b>4</b> could not be obtained, DFT calculations at the UBP86/6–311G(2d,p) level have been carried out and indicate that the cation in <b>4</b> is square pyramidal with the phosphine at the apex. The ease of the oxidation of the metal in <b>1</b> leads to the stabilization of the rare Cu(II)-P bond in <b>4</b>.</p

Steric Effects on Uranyl Complexation: Synthetic, Structural, and Theoretical Studies of Carbamoyl Pyrazole Compounds of the Uranyl(VI) Ion

New bifunctional pyrazole based ligands of the type [C₃HR₂N₂CONR′] (where R = H or CH₃; R′ = CH₃, C₂H₅, or ⁱC₃H₇) were prepared and characterized. The coordination chemistry of these ligands with uranyl nitrate and uranyl bis­(dibenzoyl methanate) was studied with infrared (IR), ¹H NMR, electrospray-mass spectrometry (ES-MS), elemental analysis, and single crystal X-ray diffraction methods. The structure of compound [UO₂(NO₃)₂(C₃H₃N₂CON­{C₂H₅}₂)] (<b>2</b>) shows that the uranium­(VI) ion is surrounded by one nitrogen atom and seven oxygen atoms in a hexagonal bipyramidal geometry with the ligand acting as a bidentate chelating ligand and bonds through both the carbamoyl oxygen and pyrazolyl nitrogen atoms. In the structure of [UO₂(NO₃)₂(H₂O)₂(C₅H₇N₂CON {C₂H₅}₂)₂], (<b>5</b>) the pyrazole ligand acts as a second sphere ligand and hydrogen bonds to the water molecules through carbamoyl oxygen and pyrazolyl nitrogen atoms. The structure of [UO₂(DBM)₂C₃H₃N₂CON­{C₂H₅}₂] (<b>8</b>) (where DBM = C₆H₅COCHCOC₆H₅) shows that the pyrazole ligand acts as a monodentate ligand and bonds through the carbamoyl oxygen to the uranyl group. The ES-MS spectra of <b>2</b> and <b>8</b> show that the ligand is similarly bonded to the metal ion in solution. Ab initio quantum chemical studies show that the steric effect plays the key role in complexation behavior

Impact of Ligand Framework on the Crystal Structures and Luminescent Properties of Cu(I) and Ag(I) Clusters and a Coordination Polymer Derived from Thiolate/Iodide/dppm Ligands

New homoleptic hexanuclear Ag­(I) and heteroleptic trinuclear Cu­(I) clusters and a Cu­(I) coordination polymer (CP) of the formulas [Ag₆(dtc)₆] <b>1</b>, [Cu₃I₂(dppm)₃(dtc)] <b>2</b>, and [Cu­(ttc)­I]_∞ <b>3</b> (dtc = <i>N</i>-methylbenzyl-<i>N</i>-methyl-thiophenedithiocarbamate; dppm = 1,1-bis­(diphenylphosphino)­methane; and ttc = dimethyltrithiocarbonate) were synthesized and characterized by elemental analysis, IR, UV–vis, ¹H, ¹³C, and ³¹P NMR spectroscopies, and their structures were elucidated by X-ray crystallography. The complexes show interesting structures and luminescent properties. Complex <b>1</b>, which is centrosymmetric, contains four short Ag···Ag interactions at 2 × 2.966(1) and 2 × 3.014(1) Å. There are also several Ag···Ag distances of 3.3–3.4 Å. The molecule shows hexagonal orientation with alternating silver and sulfur atoms of the overlapping Ag₃S₃ hexagons in the front and rear, along the <i>a</i> axis. Complex <b>2</b> is a rare trinuclear cluster complex of Cu­(I); the Cu···Cu distances are 2.906(2), 3.551(2), and 3.338(2) Å, the foremost representing a substantial intermetallic contact. The Cu₃I₂P₆S₂ core is comprised of three fused distorted hexagonal rings with the I1 atom located at the center participating in all three rings. Complex <b>3</b> is an iodide-bridged CP with a “staircase”-like arrangement in which the Cu­(I) is tetrahedrally surrounded by a sulfur atom from the ttc ligand and three iodine atoms. Unlike <b>3</b>, which is nonluminescent, <b>1</b> and <b>2</b> are strongly luminescent in the solid and solution at room temperature. The time-resolved emission spectra reveal a triexponential decay curve and short mean lifetime characteristic of fluorescence behavior. Diffuse reflectance spectroscopy revealed semiconducting behavior with band gaps of 2.12, 3.01, and 2.18 eV for <b>1</b>–<b>3</b>, respectively

Insertion of a Hydroxido Bridge into a Diphenoxido Dinuclear Copper(II) Complex: Drastic Change of the Magnetic Property from Strong Antiferromagnetic to Ferromagnetic and Enhancement in the Catecholase Activity

A diphenoxido-bridged dinuclear copper­(II) complex, [Cu₂L₂(ClO₄)₂] (<b>1</b>), has been synthesized using a tridentate reduced Schiff base ligand, 2-[[2-(diethylamino)­ethylamino]­methyl]­phenol (HL). The addition of triethylamine to the methanolic solution of this complex produced a novel triple bridged (double phenoxido and single hydroxido) dinuclear copper­(II) complex, [Cu₂L₂(OH)]­ClO₄ (<b>2</b>). Both complexes <b>1</b> and <b>2</b> were characterized by X-ray structural analyses, variable-temperature magnetic susceptibility measurements, and spectroscopic methods. In <b>1</b>, the two phenoxido bridges are equatorial–equatorial and the species shows strong antiferromagnetic coupling with <i>J</i> = −615.6(6.1) cm^–1. The inclusion of the equatorial–equatorial hydroxido bridge in <b>2</b> changes the Cu···Cu distance from 3.018 Å (avg.) to 2.798 Å (avg.), the positions of the phenoxido bridges to axial–equatorial, and the magnetic coupling to ferromagnetic with <i>J</i> = 50.1(1.4) cm^–1. Using 3,5-di-<i>tert</i>-butylcatechol as the substrate, the catecholase activity of the complexes has been studied in a methanol solution; compound <b>2</b> shows higher catecholase activity (<i>k</i>_cat = 233.4 h^–1) than compound <b>1</b> (<i>k</i>_cat = 93.6 h^–1). Both complexes generate identical species in solution, and they are interconvertible simply by changing the pH of their solutions. The higher catecholase activity of <b>2</b> seems to be due to the presence of the OH group, which increases the pH of its solution

A Ferromagnetic Methoxido-Bridged Mn(III) Dimer and a Spin-Canted Metamagnetic μ_1,3-Azido-Bridged Chain

Two new Mn­(III) complexes of formulas [MnL¹(N₃)­(OMe)]₂ (<b>1</b>) and [MnL²(N₃)₂]_<i>n</i> (<b>2</b>) have been synthesized by using two tridentate NNO-donor Schiff base ligands HL¹{(2-[(3-methylaminoethylimino)-methyl]-phenol)} and HL² {(2-[1-(2-dimethylaminoethylimino)­methyl]­phenol)}, respectively. Substitution of the H atom on the secondary amine group of the N-methyldiamine fragment of the Schiff base by a methyl group leads to a drastic structural change from a methoxido-bridged dimer (<b>1</b>) to a single μ_1,3-azido-bridged 1D helical polymer (<b>2</b>). Both complexes were characterized by single-crystal X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The magnetic properties of compound <b>1</b> show the presence of weak ferromagnetic exchange interactions mediated by double methoxido bridges (<i>J</i> = 0.95 cm^–1). Compound <b>2</b> shows the existence of a weak antiferromangetic coupling along the chain (<i>J</i> = −8.5 cm^–1) through the single μ_1,3-N₃ bridge with a spin canting that leads to a long-range antiferromagnetic order at <i>T</i>_c ≈ 9.3 K and a canting leading to a weak ferromagnetic long-range order at <i>T</i>_c ≈ 8.5 K. It also exibits metamagnetic behavior at low temperatures with a critical field of ca.1.2 T due to the weak antiferromagnetic interchain interactions that appear in the canted ordered phase

A Ferromagnetic Methoxido-Bridged Mn(III) Dimer and a Spin-Canted Metamagnetic μ_1,3-Azido-Bridged Chain

Two new Mn­(III) complexes of formulas [MnL¹(N₃)­(OMe)]₂ (<b>1</b>) and [MnL²(N₃)₂]_<i>n</i> (<b>2</b>) have been synthesized by using two tridentate NNO-donor Schiff base ligands HL¹{(2-[(3-methylaminoethylimino)-methyl]-phenol)} and HL² {(2-[1-(2-dimethylaminoethylimino)­methyl]­phenol)}, respectively. Substitution of the H atom on the secondary amine group of the N-methyldiamine fragment of the Schiff base by a methyl group leads to a drastic structural change from a methoxido-bridged dimer (<b>1</b>) to a single μ_1,3-azido-bridged 1D helical polymer (<b>2</b>). Both complexes were characterized by single-crystal X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The magnetic properties of compound <b>1</b> show the presence of weak ferromagnetic exchange interactions mediated by double methoxido bridges (<i>J</i> = 0.95 cm^–1). Compound <b>2</b> shows the existence of a weak antiferromangetic coupling along the chain (<i>J</i> = −8.5 cm^–1) through the single μ_1,3-N₃ bridge with a spin canting that leads to a long-range antiferromagnetic order at <i>T</i>_c ≈ 9.3 K and a canting leading to a weak ferromagnetic long-range order at <i>T</i>_c ≈ 8.5 K. It also exibits metamagnetic behavior at low temperatures with a critical field of ca.1.2 T due to the weak antiferromagnetic interchain interactions that appear in the canted ordered phase

Heterooctamolybdate-Based Clusters H₃[(Cp*Rh)₄PMo₈O₃₂] and H₅[Na₂(Cp*Ir)₄PMo₈O₃₄] and Derived Hybrid Nanomaterials with Efficient Electrocatalytic Hydrogen Evolution Reaction Activity

Polyoxometalates (POMs), emerging as a new class of porous molecular materials, play a promising role in homo- and heterogeneous catalysis. Among them, noble-metal-decorated POMs have a profound impact as catalytic materials. Thus, it is imperative to design and structurally explore new catalysts including noble metals. Herein, two new clusters, H₃[(Cp*Rh)₄PMo₈O₃₂]·14H₂O (<b>1</b>) and H₅[Na₂(Cp*Ir)₄PMo₈O₃₄]·13H₂O (<b>2</b>) (Cp* = pentamethylcyclopentadienyl), based on a heterooctamolybdate anionic core were successfully obtained via a one-pot reaction using [Cp*MCl₂]₂ [M = Rh (<b>1</b>) and Ir (<b>2</b>)] and Na₂MoO₄ in acidic conditions. Compounds <b>1</b> and <b>2</b> were well characterized in the solid state by single-crystal X-ray diffraction, IR, and thermogravimetric analysis and in solution by UV–vis, electrospray ionization mass spectrometry, and electrochemistry. Compounds <b>1</b> and <b>2</b> represent an important class of structurally isolated organometallic POM-based clusters that were successfully nanostructured onto Ni foam and electrochemically reduced after 48 h of electrolysis to M/MoO₂, where M = Rh (<b>3</b>) and Ir (<b>4</b>), nanocomposite hybrid materials on a Ni foam surface in a 0.1 M KOH solution. The modified electrocatalysts (<b>3</b> and <b>4</b>) show efficient hydrogen evolution reaction activities almost comparable to those of high-grade Pt/C at 0.1 M KOH. The nanostructured POMs [<b>1</b>- and <b>2</b>@NF (Ni foam)] and their corresponding reduced products (<b>3</b> and <b>4</b>) were observed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy and further proven by transmission electron microscopy (TEM) and high-resolution TEM