Synthesis and structural characterisation of a novel tris-methylene bridged compound (NO) 4Fe2 Se(μ-CH2)3

The tris-methylene bridged compound (NO)₄Fe₂Se(μ-CH₂)₃ has been isolated. It has been characterised by IR and ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups.     

Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3

Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.     

Structure determination of bioactive galloyl derivatives by NMR spectroscopy

The investigation of the chemical constituents of Symplocos racemosa Roxb led to the isolation of two new glycosides, symcomoside A (1) and symcomoside B (2), together with one known glycoside, tortoside C (3), which is reported for the first time from this plant. The structures of the new compounds were determined by 1D and 2D homonuclear and heteronuclear NMR spectroscopy, from chemical evidence and by comparison with published data for closely related compounds. Symcomoside B (2) showed potent inhibitory activity against alpha-glucosidase in a concentration-dependent fashion with an IC50 value of 0.733 +/- 0.033 mM whereas symcomoside A (1) showed very weak inhibitory activity against alpha-glucosidase (9.90% in 0.70 mM).     

Electronic phase separation in transition metal oxide systems

Electronic phase separation is increasingly getting recognized as a phenomenon of importance in understanding the magnetic and electron transport properties of transition metal oxides. The phenomenon dominates the rare-earth manganates of the formula Ln(1-x)A(x)MnO(3)(Ln = rare earth and A = alkaline earth) which exhibit ferromagnetism and metallicity as well as charge-ordering, depending on the composition, size of A-site cations and external factors such as magnetic and electric fields. We discuss typical phase separation scenarios in the manganates, with particular reference to Pr(1-x)Ca(x)MnO(3)(x= 0.3-0.4), (La(1-x)Ln(x))(0.7)Ca(0.3)MnO(3)(Ln = Pr, Nd, Gd and Y) and Nd(0.5)Sr(0.5)MnO(3). Besides discussing the magnetic and electron transport properties, we discuss electric field effects. Rare-earth cobaltates of the type Pr(0.7)Ca(0.3)CoO(3) and Gd(0.5)Ba(0.5)CoO(3) also exhibit interesting magnetic and electron transport properties which can be understood in terms of phase separation.     

Synthesis,structure, and magnetic properties of dinuclear cobalt(II) complexes with a new phenol-based dinucleating ligand with four hydroxyethyl chelating arms

A new end-off type acyclic ligand with four hydroxyethyl arms, 2,6-bis[bis(2-hydroxyethyl)aminomethyl]-4-methylphenol [H(bhmp)], formed dinuclear cobalt(II) complexes [Co(2)(bhmp)(OAc)(2)]BPh(4) (1) and [Co(2)(bhmp)(OBz)(2)]BPh(4) (2). The complex 1.2.5CH(3)CN (C(50)H(62.5)BCo(2)N(4.5)O(9)) crystallizes in the monoclinic space group C2/c with dimensions a = 25.424(5) A, b = 13.376(2) A, c = 29.913(6) A, beta = 105.930(3) degrees, and V = 9781(3) A(3) and with Z = 8. X-ray diffraction analysis revealed a mu-phenoxo-bis(mu-acetato)dicobalt(II) core structure containing two octahedral cobalt(II) ions. Electronic spectra were investigated for 1 and 2 in the range 400-1800 nm, and the data were typical for the octahedral high-spin cobalt(II) complexes. Magnetic susceptibility was measured for 1 and 2 over the temperature range 4.5-300 K, and the data were analyzed well using our theoretical method. The best fitting parameters were kappa = 0.77, lambda = -116 cm(-1), Delta = 572 cm(-1), and J = -0.44 cm(-1) for complex 1 and kappa = 0.96, lambda = -93 cm(-1), Delta = 616 cm(-1), and J = -0.33 cm(-1) for complex 2.     

4,7‐Diiodo‐2,1,3‐benzothiadiazole and 7,7′‐diiodo‐4,4′‐bi(2,1,3‐benzothiadiazole)

In the crystal structures of the title compounds, C₆H₂I₂N₂S, (I), and C₁₂H₄I₂N₄S₂, (II), respectively, a large number of short inter‐heteroatom contacts, such as S?N, I?I and N?I, are observed. In (II), which is non‐centrosymmetric, two halves of the mol­ecule are related by a crystallographic twofold axis.     

Influence of conjugated nitrogenous bases on the spectra and structure of mixed-ligand nickel(II) chelates containing β-diones

The infrared and electronic excitation spectra of a series of new nickel(II) chelates containing an-diimine (or nitrogenous base, enR) and the anion of a-dione (1,3-ketoenol or 1,3-ketoester,H) were obtained in the solid state and in solution. The composition and the overall structure of the new chelates in the solid state depends on ligand concentration, the substituents within the-dionato moiety and the counterion present. The IR and electronic excitation spectra of [Ni(enR)₂ ]NO₃ and [Ni(enR)(O₂NO)] indicate, in conjunction with other physicochemical measurements, bidentate coordination of the ligands, while the spectral shifts reveal replacement of the (O,O)nitrato group by basic solvents. The existence of the nickel(II) in an octahedral environment is confirmed by an X-ray structure analysis of [Ni(dpamH)₂acac]NO₃ · CH₃OH (monoclinic, space groupP2_l/n, a=17.296(1),b=7.462(1),c=21.604(3) å,=95.65(1),Z=4, R=0.0534,Rw=0.0600), where dpamH denotes the 2,2-dipyridylamine.     

Some spectroscopic aspects of electron transfer in ruthenium(II) polypyridyl complexes

The metal-to-ligand charge transfer (MLCT) absorption and emission properties of several ruthenium(II)-bipyridine am(m)ine complexes are compared. The Gaussian deconvolution of the spectra indicates that: (a) the emission MLCT bandwidths are smaller than the absorption bandwidths for the first components of the apparent vibronic progressions; (b) the emission bands decrease in energy and width when a polypyridyl is replaced by an am(m)ine. The observations can be interpreted in terms of a two state model and the perturbation theory-based treatment of the attenuation of the effective reorganizational energy, λ_r =^~ λ_r ^o(1- 4α² _DA), where λ_r ^o is the reorganizational energy corresponding to no mixing between the two electron transfer states and α_DA = (H_DA/E_DA) is the mixing coefficient. Both the solvent and molecular contributions to λ_r are attenuated. The MLCT excited state lifetimes also decrease with am(m)ine substitution, and the non-radiative decay rate constant at 77 K is roughly proportional to the number of am(m)ine moieties coordinated to the ruthenium center.     

Long Duration Persistent Photocurrent in 3 nm Thin Doped Indium Oxide for Integrated Light Sensing and In-Sensor Neuromorphic Computation

Miniaturization and energy consumption by computational systems remain major challenges to address. Optoelectronics based synaptic and light sensing provide an exciting platform for neuromorphic processing and vision applications offering several advantages. It is highly desirable to achieve single-element image sensors that allow reception of information and execution of in-memory computing processes while maintaining memory for much longer durations without the need for frequent electrical or optical rehearsals. In this work, ultra-thin (<3 nm) doped indium oxide (In₂O₃) layers are engineered to demonstrate a monolithic two-terminal ultraviolet (UV) sensing and processing system with long optical state retention operating at 50 mV. This endows features of several conductance states within the persistent photocurrent window that are harnessed to show learning capabilities and significantly reduce the number of rehearsals. The atomically thin sheets are implemented as a focal plane array (FPA) for UV spectrum based proof-of-concept vision system capable of pattern recognition and memorization required for imaging and detection applications. This integrated light sensing and memory system is deployed to illustrate capabilities for real-time, in-sensor memorization, and recognition tasks. This study provides an important template to engineer miniaturized and low operating voltage neuromorphic platforms across the light spectrum based on application demand.     

Deterministic Polymorphic Engineering of MoTe2 for Photonic and Optoelectronic Applications

Developing selective and coherent polymorphic crystals at the nanoscale offers a novel strategy for designing integrated architectures for photonic and optoelectronic applications such as metasurfaces, optical gratings, photodetectors, and image sensors. Here, a direct optical writing approach is demonstrated to deterministically create polymorphic 2D materials by locally inducing metallic 1T′-MoTe₂ on the semiconducting 2H-MoTe₂ host layer. In the polymorphic-engineered MoTe₂, 2H- and 1T′- crystalline phases exhibit strong optical contrast from near-infrared to telecom-band ranges (1–1.5 µm), due to the change in the band structure and increase in surface roughness. Sevenfold enhancement of third harmonic generation intensity is realized with conversion efficiency (susceptibility) of ≈1.7 × 10⁻⁷ (1.1 × 10⁻¹⁹ m² V⁻²) and ≈1.7 × 10⁻⁸ (0.3 × 10⁻¹⁹ m² V⁻²) for 1T′ and 2H-MoTe₂, respectively at telecom-band ultrafast pump laser. Lastly, based on polymorphic engineering on MoTe₂, a Schottky photodiode with a high photoresponsivity of 90 AW⁻¹ is demonstrated. This study proposes facile polymorphic engineered structures that will greatly benefit realizing integrated photonics and optoelectronic circuits.