Quasi-ternary nanoparticle superlattices through nanoparticle design

Individual nanoscale building blocks exhibit a wide range of size-dependent properties, since their size can be tuned over known characteristic length scales of bulk materials. In the last several years, the possibility of combining different materials in the form of two and three component nanoparticles (NPs) has been extensively explored. Also multi-component materials can be obtained via self-assembly of NPs from their binary colloidal mixtures. These new nanocrystal solids may possess tunable collective properties that originate from interactions between size and composition controlled building blocks. Exchange coupling between neighboring NPs of magnetically soft and hard materials enhances the magnetic energy product of the nanocomposite material. Randomly mixed solids of small and large semiconducting CdSe NPs revealed enhancement of photoluminescence intensity of large semiconductor particles accompanied by quenching of photoluminescence of the small particles because of long-range resonant transfer of electronic excitations from the more electronically confined small particles to higher excited states of the large particles. Recently, it was demonstrated that binary semiconducting composite materials can show strongly enhanced electronic properties with about 100-fold higher conductance as compared to the sum of individual conductances of single-component films. Creation of highly periodic superlattices is expected not just provide the control of the homogeneity of the sample but also affect their properties. It was shown that silver nanocrystals organized into periodic cubic structures vibrated coherently [20] and demonstrated a change in electronic transport properties

Bonding, Backbonding, and Spin-Polarized Molecular Orbitals:Basis for Magnetism and Semiconducting Transport in V[TCNE]x~;;2

X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (MCD) at the V L2,3 and C and N K edges reveal bonding/backbonding interactions in films of the 400 K magnetic semiconductor V[TCNE]x~;;2. In V spectra, dxy-like orbitals are modeled assuming V2+ in an octahedral ligand field, while dz2 and dx2-y2 orbitals involved in strong covalent bonding cannot be modeled by atomic calculations. C and N MCD, and differences in XAS from neutral TCNE molecules, reveal spin-polarized molecular orbitals in V[TCNE]x~;;2 associated with backbonding interactions that yield its novel properties

Probing Adsorption Interactions in Metal-Organic Frameworks using X-ray Spectroscopy

We explore the local electronic signatures of molecular adsorption at coordinatively unsaturated binding sites in the metal-organic framework Mg-MOF-74 using X-ray spectroscopy and first-principles calculations. In situ measurements at the Mg K-edge reveal distinct pre-edge absorption features associated with the unique, open coordination of the Mg sites which are suppressed upon adsorption of CO2 and N,N′-dimethylformamide. Density functional theory shows that these spectral changes arise from modifications of local symmetry around the Mg sites upon gas uptake and are strongly dependent on the metal-adsorbate binding strength. The expanded MOF Mg2(dobpdc) displays the same behavior upon adsorption of CO 2 and N,N′-dimethylethylenediamine. Similar sensitivity to local symmetry is expected for any open metal site, making X-ray spectroscopy an ideal tool for examining adsorption in such MOFs. Qualitative agreement between ambient-temperature experimental and 0 K theoretical spectra is good, with minor discrepancies thought to result from framework vibrational motion. © 2013 American Chemical Society

Bonding, Backbonding, and Spin-Polarized Molecular Orbitals: Basis for Magnetism and Semiconducting Transport in V[TCNE]x~;;2

X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (MCD) at the V L2,3 and C and N K edges reveal bonding/backbonding interactions in films of the 400 K magnetic semiconductor V[TCNE]x~;;2. In V spectra, dxy-like orbitals are modeled assuming V2+ in an octahedral ligand field, while dz2 and dx2-y2 orbitals involved in strong covalent bonding cannot be modeled by atomic calculations. C and N MCD, and differences in XAS from neutral TCNE molecules, reveal spin-polarized molecular orbitals in V[TCNE]x~;;2 associated with backbonding interactions that yield its novel properties