Doping of metal–organic frameworks towards resistive sensing

Coordination polymerization leads to various metal–organic frameworks (MOFs) with unique physical properties and chemical functionalities. One of the challenges towards their applications as porous materials is to make MOFs optimally conductive to be used as electronic components. Here, it is demonstrated that Co-MOF-74, a honeycomb nano–framework with one–dimensionally arranged cobalt atoms, advances its physical properties by accommodating tetracyanochinodimethan (TCNQ), an acceptor molecule. Strong intermolecular charge transfer reduces the optical band gap down to 1.5 eV of divalent TCNQ and enhances the electrical conduction, which allows the MOF to be utilized for resistive gas- and photo-sensing. The results provide insight into the electronic interactions in doped MOFs and pave the way for their electronic applications.© The Author(s) 201

Nickel clusters embedded in carbon nanotubes as high performance magnets

Ensembles of fcc nickel nanowires have been synthesized with defined mean sizes in the interior of single-wall carbon nanotubes. The method allows the intrinsic nature of single-domain magnets to emerge with large coercivity as their size becomes as small as the exchange length of nickel. By means of X-ray magnetic circular dichroism we probe electronic interactions at nickel-carbon interfaces where nickel exhibit no hysteresis and size-dependent spin magnetic moment. A manifestation of the interacting two subsystems on a bulk scale is traced in the nanotube’s magnetoresistance as explained within the framework of weak localization

Exchange coupling in a frustrated trimetric molecular magnet reversed by a 1D nano-confinement

Single-molecule magnets exhibit magnetic ordering due to exchange coupling between localized spin components that makes them primary candidates as nanometric spintronic elements. Here we manipulate exchange interactions within a single-molecule magnet by nanometric structural confinement, exemplified with single-wall carbon nanotubes that encapsulate trimetric nickel(II) acetylacetonate hosting three frustrated spins. It is revealed from bulk and Ni 3d orbital magnetic susceptibility measurements that the carbon tubular confinement allows a unique one-dimensional arrangement of the trimer in which the nearest-neighbour exchange is reversed from ferromagnetic to antiferromagnetic, resulting in quenched frustration as well as the Pauli paramagnetism is enhanced. The exchange reversal and enhanced spin delocalisation demonstrate the means of mechanically and electrically manipulating molecular magnetism at the nanoscale for nano-mechatronics and spintronics

Chirality-dependent growth of single-wall carbon nanotubes as revealed inside nano-test tubes

Growth dynamics of single-wall carbon nanotubes (SWCNTs) have been studied with nickelocene as a precursor encapsulated in the interior of template SWCNTs. By means of multi-laser Raman spectroscopy, growth curves of nine different SWCNTs, (8,8), (12,3), (13,1), (9,6), (10,4), (11,2), (11,1), (9,3) and (9,2), have been determined upon in situ annealing at various temperatures. The data reveal that the nanotubes grow through fast and slow reaction pathways with high and low activation energies, respectively. While the activation energy of the slow growth is independent of the nanotube's chiral vector, that of the fast growth exhibits a monotonic increase as the tube diameter reduces from ∼1.1 down to 0.8 nm and no dependency on the chiral angle, which can be attributed to the size-dependent properties of catalyst clusters. The chirality dependent catalytic growth properties exploited in this study provide the basis for a large-scale synthesis of single-chiral vector SWCNTs