Planar π-extended cycloparaphenylenes featuring an all-armchair edge topology.

The [n]cycloparaphenylenes ([n]CPPs)-n para-linked phenylenes that form a closed-loop-have attracted substantial attention due to their unique cyclic structure and highly effective para-conjugation leading to a myriad of fascinating electronic and optoelectronic properties. However, their strained topology prevents the π-extension of CPPs to convert them either into armchair nanobelts or planarized CPP macrocycles. Here we successfully tackle this long-standing challenge and present the bottom-up synthesis and characterization of atomically precise in-plane π-extended [12]CPP on Au(111) by low-temperature scanning probe microscopy and spectroscopy combined with density functional theory. The planar π-extended CPP is a nanographene with an all-armchair edge topology. The exclusive para-conjugation at the periphery yields delocalized electronic states and the planarization maximizes the overlap of p orbitals, which both reduce the bandgap compared to conventional CPPs. Calculations predict ring currents and global aromaticity in the doubly charged system. The intriguing planar ring topology and unique electronic properties make planar π-extended CPPs promising quantum materials.

Site selective adsorption of the spin crossover complex Fe(phen)2(NCS) on Au(111).

The iron(II) spin crossover complex Fe(1,10-phenanthroline)2(NCS)2, dubbed Fe-phen, has been studied with scanning tunneling microscopy, after adsorption on the 'herringbone' reconstructed surface of Au(111) for sub-monolayer coverages. The Fe-phen molecules attach, through their NCS-groups, to the Au atoms of the fcc domains of the reconstructed surface only, thereby lifting the herringbone reconstruction. The molecules stack to form 1D chains, which run along the Au[110] directions. Neighboring Fe-phen molecules are separated by approximately 2.65 nm, corresponding to 9 atomic spacings in this direction. The molecular axis, defined by the two phenanthroline groups, is aligned perpendicular to the chain axis, along the Au [Formula: see text] direction, thereby bridging over 5 atomic spacings, in this direction. Experimental evidence suggests that the molecular spins are locked in a mixed state in the sub-monolayer regime at temperatures between 100 K and 300 K.

Coordination-Controlled C-C Coupling Products via ortho-Site C-H Activation.

The coordination-restricted ortho-site C-H bond activation and dehydrogenative homocoupling of 4,4'-(1,3-phenylene)dipyridine (1,3-BPyB) and 4,4'-(1,4-phenylene)dipyridine (1,4-BPyB) on different metal surfaces were studied by a combination of scanning tunneling microscopy, noncontact atomic force microscopy, and density functional theory calculations. The coupling products on Cu(111) exhibited certain configurations subject to the spatial restriction of robust two-fold Cu-N coordination bonds. Compared to the V-shaped 1,3-BPyB, the straight backbone of 1,4-BPyB helped to further reduce the variety of reactive products. By utilizing the three-fold coordination of Fe atoms with 1,4-BPyB molecules on Au(111), a large-scale network containing single products was constructed. Our results offer a promising protocol for controllable on-surface synthesis with the aid of robust coordination interactions.

Magnetism of new metastable cobalt-nitride compounds.

The search for new magnetic materials with high magnetization and magnetocrystalline anisotropy is important for a wide range of applications including information and energy processing. There is only a limited number of naturally occurring magnetic compounds that are suitable. This situation stimulates an exploration of new phases that occur far from thermal-equilibrium conditions, but their stabilization is generally inhibited due to high positive formation energies. Here a nanocluster-deposition method has enabled the discovery of a set of new non-equilibrium Co-N intermetallic compounds. The experimental search was assisted by computational methods including adaptive-genetic-algorithm and electronic-structure calculations. Conventional wisdom is that the interstitial or substitutional solubility of N in Co is much lower than that in Fe and that N in Co in equilibrium alloys does not produce materials with significant magnetization and anisotropy. By contrast, our experiments identify new Co-N compounds with favorable magnetic properties including hexagonal Co3N nanoparticles with a high saturation magnetic polarization (Js = 1.28 T or 12.8 kG) and an appreciable uniaxial magnetocrystalline anisotropy (K1 = 1.01 MJ m-3 or 10.1 Mergs per cm3). This research provides a pathway for uncovering new magnetic compounds with computational efficiency beyond the existing materials database, which is significant for future technologies.

Locking and Unlocking the Molecular Spin Crossover Transition.

The Fe(II) spin crossover complex [Fe{H2 B(pz)2 }2 (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO2 and Al2 O3 , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C6 H2 (-⋯ NH2 )2 (-⋯ O)2 . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H2 B(pz)2 }2 (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.

Graphene-like Boron-Carbon-Nitrogen Monolayers.

A strategy to synthesize a 2D graphenic but ternary monolayer containing atoms of carbon, nitrogen, and boron, h-BCN, is presented. The synthesis utilizes bis-BN cyclohexane, B2N2C2H12, as a precursor molecule and relies on thermally induced dehydrogenation of the precursor molecules and the formation of an epitaxial monolayer on Ir(111) through covalent bond formation. The lattice mismatch between the film and substrate causes a strain-driven periodic buckling of the film. The structure of the film and its corrugated morphology is discussed based on comprehensive data from molecular-resolved scanning tunneling microscopy imaging, X-ray photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. First-principles calculations further predict a direct electronic band gap that is intermediate between gapless graphene and insulating h-BN.

2D Cocrystallization from H-Bonded Organic Ferroelectrics.

The synthesis of 2D H-bonded cocrystals from the room-temperature ferroelectric organics croconic acid (CA) and 3-hydroxyphenalenone (3-HPLN) is demonstrated through self-assembly on a substrate under ultrahigh vacuum. 2D cocrystal polymorphs of varied stoichiometry were identified with scanning tunneling microscopy, and one of the observed structural building blocks consists of two CA and two 3-HPLN molecules. Computational analysis with density functional theory confirmed that the experimental (CA)2(3-HPLN)2 tetramers are lower in energy than single-component structures due to the ability of the tetramers to pack efficiently in two dimensions, the promotion of favorable electrostatic interactions between tetramers, and the optimal number of intermolecular hydrogen bonds. The structures investigated, especially the experimentally found tetrameric building blocks, are not polar. However, it is demonstrated computationally that cocrystallization can, in principle, result in heterogeneous structures with dipole moments that exceed those of homogeneous structures and that 2D structures with select stoichiometries could favor metastable polar structures.

Self-assembly of strongly dipolar molecules on metal surfaces.

The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(⋯ NHR)2(⋯ O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings.

HIV-associated dementia: A diagnostic dilemma.

BACKGROUND: Considerable clinical research has been conducted to increase our knowledge in understanding the underlying neuropathological significance of HIV viral infection. AIM: To find the incidence of HIV Associated Dementia in a suburban part of India. MATERIALS AND METHODS: 6135 prospective cases from January 2008 to August 2010 were subjected to pretest counseling. Those willing were tested for HIV status using western blot test. RESULTS: 5688 (92.71%) underwent for detection of HIV.273 (4.8%) were tested positive. 246 out of these (90.10%) were put on ART. 1 (0.37%) was detected to have HAD stage II.38 cases (18.92%) had varied psychiatric symptoms. CONCLUSION: HAART has considerably reduced morbidity in HIV infection.