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We report synthesis and luminescent characteristics of core-shell nanostructures of silicon and silicon oxide having two different morphologies—spherical (nanodot) and rodlike (nanorod), prepared by controlled oxidation of mechanically milled crystalline silicon and by exfoliation of the affected layer of porous silicon. Colloidal suspensions of these nanostructures exhibit intense room temperature photoluminescence (PL), detectable with the unaided eye. PL band peak energies of the colloidal suspensions formed from porous silicon are blue shifted by ∼1 eV compared to the as-prepared films on silicon substrate. In addition, PL spectra of all the colloidal suspensions blueshift with increase in excitation energy but the PL peaks of as-prepared porous silicon are independent of excitation. However, shape of the nanocrystals (spherical or rodlike) is found to have little effect on the emission spectra. These observations are explained in terms discretization of phonon density of states and electronic transitions involving surface defect states and quantum confinement induced widened band states.

Single layer graphite, known as graphene, is an important material because of its unique two-dimensional structure, high conductivity, excellent electron mobility and high surface area. To explore the more prospective properties of graphene, graphene hybrids have been synthesised, where graphene has been integrated with other important nanoparticles (NPs). These graphene–NP hybrid structures are particularly interesting because after hybridisation they not only display the individual properties of graphene and the NPs, but also they exhibit further synergistic properties. Reduced graphene oxide (rGO), a graphene-like material, can be easily prepared by reduction of graphene oxide (GO) and therefore offers the possibility to fabricate a large variety of graphene–transition metal oxide (TMO) NP hybrids. These hybrid materials are promising alternatives to reduce the drawbacks of using only TMO NPs in various applications, such as anode materials in lithium ion batteries (LIBs), sensors, photocatalysts, removal of organic pollutants, etc. Recent studies have shown that a single graphene sheet (GS) has extraordinary electronic transport properties. One possible route to connecting those properties for application in electronics would be to prepare graphene-wrapped TMO NPs. In this critical review, we discuss the development of graphene–TMO hybrids with the detailed account of their synthesis. In addition, attention is given to the wide range of applications. This review covers the details of graphene–TMO hybrid materials and ends with a summary where an outlook on future perspectives to improve the properties of the hybrid materials in view of applications are outlined.

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are discussed/compared in this study. Four types of composition are observed in the Cu(II)Ln(III) complexes: [Cu(II)LLn(III) (NO(3))(3)(H(2)O)] (1-3: Ln = Ce-Nd), [Cu(II)LSm(III)(NO(3))(3)]·CH(3)COCH(3) (4), [Cu(II)(H(2)O)LLn(III)(NO(3))(3)] (5: Ln = Eu; 6: Ln = Gd), and [Cu(II)LLn(III)(NO(3))(3)] (4A: Ln = Sm; 7-12: Ln = Tb-Yb). On the other hand, the Ni(II)Ln(III) complexes are characterized to have two types of composition: [Ni(II)LLn(III)(H(2)O)(NO(3))(3)] (13-15: Ln = Ce-Nd) and [Ni(II)LLn(III)(NO(3))(3)]·0.5CH(3)COCH(3) (16-24: Ln = Sm-Yb). Among twelve X-ray structures, seven belong to three different isomorphous sets (Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13); Cu(II)Tb(III) (7), Cu(II)Ho(III) (9), Cu(II)Er(III) (10), and Cu(II)Yb(III) (12); Ni(II)Sm(III) (16) and Ni(II)Gd(III) (18)), whereas space group/unit cell parameters of two others (Cu(II)Sm(III) (4) and Cu(II)Gd(III) (6)) are of different types. The lanthanide(III) centers in Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13) complexes are eleven-coordinated, while the lanthanide(III) centers in other compounds are ten-coordinated. As evidenced from the dihedral angle (δ) between the CuO(phenoxo)(2) and LnO(phenoxo)(2) planes, variation in the extent of planarity of the bridging moiety in the Cu(II)Ln(III) compounds takes place; the ranges of δ values are 0.8-6.2° in the 4f(1-7) analogues and 17.6-19.1° in the 4f(8-13) analogues. The Cu(II)Gd(III) (6) compound exhibits ferromagnetic interaction (Eur. J. Inorg. Chem. 2005, 1500). The nature of the magnetic exchange interaction in the Cu(II)Ln(III) complexes has been understood by utilizing the empirical approach; the Ni(II)Ln(III) complexes have been used as references. The metal centers in the Eu(III) complex are uncorrelated, while other 4f(1-6) analogues (Ce(III), Pr(III), Nd(III), and Sm(III)) exhibit antiferromagnetic interaction. Among the higher analogues (4f(7-13)), only Yb(III) exhibits antiferromagnetic interaction, while interaction in other analogues (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), and Tm(III)) is ferromagnetic. An important aspect of the present study is the measurement of the magnetic susceptibility of the unblocked samples as well as on blocking the samples with grease to avoid powder reorientation, if any. Comparison of the ...

The journey of the syntheses and studies of the structures and properties of metal complexes derived from double-compartment 3-ethoxysalicylaldehyde-diamine (H 2 L OEt ) ligands was started in 1995, as per the CSD version 1.15 (2012) record. After dealing with mainly mononuclear complexes in the early years, the "metallo-ligand as reactant" approach was started in 2002 with the reporting of a Cu II Gd III compound, with the aim to explore the magnetic properties of 3d-4f systems. It was realized within a few years that the O(phenoxo) 2 O(ethoxy) 2 compartment has strong potential to interact with water molecule(s) due to the formation of bifurcated hydrogen bonds, resulting in the stabilization of the mononuclear inclusion products and two-component and even three-component cocrystals. "Metallo-ligand as reactant" was reacted with several metal ions from various parts of the periodic table (s, p, 3d, d 10 , 4f, 5f) as well as with possible hydrogen bond donors, such as an ammonium ion, diprotonated diamines, dicarboxylic acids and aquated proton (perchloric acid). A number of cocrystals, supramolecular dimers, a new type of hydrate isomerism, systems with interesting topologies and systems showing resemblances of entirely different types of metal ions have been obtained. Eventually, we can call the H 2 L OEt a special ligand family and the O(phenoxo) 2 O(ethoxy) 2 compartment a cosmopolitan compartment. This highlight deals with the metal complexes derived from 3-ethoxysalicylaldehyde-diamine ligands from a crystal engineering perspective.