Mixed-valent dodecanuclear vanadium cluster encapsulating chloride anions and its reaction to form a "bowl"-shaped cluster

Two oxovanadium phosphonate cage compounds have been synthesized in an organic solvent, and their characterization has been done by single-crystal X-ray analysis, IR spectroscopy, and bond valence sum calculations. The simple reaction of a mixed-valent closed V12 cage system produced another quasi-closed system composed of two V6 bowl-type cages.     

Lanthanide‐Based Layer‐Type Two‐Dimensional Coordination Polymers Featuring Slow Magnetic Relaxation,Magnetocaloric Effect and Proton Conductivity

Three lanthanide‐based two‐dimensional (2D) coordination polymers (CPs), [Ln(L)(H₂O)₂]_n, {H₃L=(HO)₂P(O)CH₂CO₂H; Ln=Dy³⁺ (CP 1 ), Er³⁺ (CP 2 )} and [{Gd₂(L)₂(H₂O)₃}^.H₂O]_n, (CP 3 ) were hydrothermally synthesized using phosphonoacetic acid as a linker. Structural features revealed that the dinuclear Ln³⁺ nodes were present in the 2D sheet of CP 1 and CP 2 while in the case of CP 3 , nodes were further connected to each other forming a chain‐type arrangement throughout the network. The magnetic studies show field‐induced slow magnetic relaxation property in CP 1 and CP 2 with U_eff values of 72 K (relaxation time, τ₀=3.05×10^?7 s) and 38.42 K (relaxation time, τ₀=4.60×10^?8 s) respectively. Ab‐initio calculations suggest that the g tensor of Kramers doublet of the lanthanide ion (Dy³⁺ and Er³⁺) is strongly axial in nature which reflects in the slow magnetic relaxation behavior of both CPs. CP 3 exhibits a significant magnetocaloric effect with ?ΔS_m=49.29 J kg^?1 K^?1, one of the highest value among the reported 2D CPs. Moreover, impedance analysis of all the CPs show high proton conductivity with values of 1.13×10^?6 S cm^?1, 2.73×10^?3 S cm^?1 and 2, 6.27×10^?6 S cm^?1 for CPs 1 – 3 , respectively, at high temperature (>75 °C) and maximum 95 % relative humidity (RH).     

Adsorption of gold on hydrogen terminated Si(0 0 1): Formation of chain structure

Possible formation of stable Au atomic wire on the hydrogen terminated Si(0 0 1): 3×1 surface is investigated under the density functional formalism. The hydrogen terminated Si(0 0 1): 3×1 surface is patterned in two different ways by removing selective hydrogen atoms from the surface. The adsorption of Au on such surfaces is studied at different sub-monolayer coverages. At 4/9 monolayer (ML) coverage, zigzag continuous Au chains are found to be stable on the patterned hydrogen terminated Si(0 0 1): 3×1 surface. The reason for the stability of the wire structures at 4/9 ML coverage is explained. It is to be noted that beyond 4/9 ML coverage, the additional Au atoms may introduce clusters on the surface. The continuous atomic gold chains on the substrate may be useful for the fabrication of atomic scale devices.     

Oxo-, hydroxo-, and peroxo-bridged Fe(III) phosphonate cages

A series of five Fe(III) phosphonate clusters with four different topologies is reported. The choice of coligand carboxylate plays an important role in directing the structure of the molecule. [Fe9(O)4(O2CCMe3)13(C10P)3] (1) and [Fe9(O)2(OH)(CO2Ph)10(C10P)6(H2O)2](CH3CN)7 (2; camphyl phosphonic acid, C10H17PO3H2 = C10PH2) represent two unprecedented nonanuclear Fe(III) cages having Fe9O4 and Fe9(O)2(OH) core structures, respectively. Whereas [Fe6O2(O)2(O2CCMe3)8(C10P)2 (H2O)2](CH3CN)4 (3) is a peroxo-bridged hexameric compound with an Fe6(O)2(O2) core. [Fe4(O)(O2CCMe3)4(C10P)3(Py)4](CH3CN)3 (4) and [Fe4(O)(O2CPh)4(C10P)3(Py)4](Py)3(CH3CN)2 (5; Py = pyridine) represents two tetranuclear clusters with the same Fe4O core structure.     

KO(t)Bu mediated synthesis of phenanthridinones and dibenzoazepinones

Synthesis of substituted phenanthridinones and dibenzoazepinones has been realized from 2-halo-benzamides in the presence of potassium tert-butoxide and a catalytic amount of 1,10-phenanthroline or AIBN. This new carbon-carbon bond forming reaction gives direct access to various biaryl lactams containing six- and seven-membered rings chemoselectively. Carbon-carbon coupling seems to proceed by the generation of a radical in the amide ring which leads to C-H arylation of aniline.     

Extremely large birefringence and shifting of zero dispersion wavelength of photonic crystal fibers

Three different types of photonic crystal fibers have been investigated which promise very large birefringence. The first type fiber is band gap guiding, the second index guiding, while the third type is index guiding with high refractive index circular and elliptical regions in the innermost ring. The birefringence, group velocity dispersion, modal effective index and mode field area of these fibers have been numerically estimated by employing finite difference time domain method. When elliptical regions are introduced in the first and second rings with the combination of small circular regions, each of these proposed fibers exhibits large birefringence with shifted zero dispersion point. Among these three different types of fibers, the band gap guiding photonic crystal fiber promises the largest birefringence (～5.45×10^?2) reported so far. The value of the birefringence and group velocity dispersion of these fibers can be controlled by controlling the hole pitch. Largest birefringence is achieved with a specific value of hole pitch.     

Strong Equatorial Crystal Field Enhances the Axial Anisotropy and Energy Barrier for Spin Reversal Process in Yb2 Single Molecule Magnets

The importance of equatorial crystal fields on magnetic anisotropy of ytterbium single molecule magnets (SMMs) is observed for the first time. Herein, we report three similar dinuclear ytterbium complexes with the formula [Yb₂(3-OMe-L)₂(DMF)₂(NO₃)₂]⋅DMF ( 1 ), [Yb₂(3-H-L)₂(DMF)₂(NO₃)₂]⋅DMF⋅H₂O ( 2 ), and [Yb₂(3-NO₃-L)₂(DMF)₂(NO₃)₂] ( 3 ), [where 3-X-H₂L=N′-(2-hydroxy-3-X-benzylidene)picolinohydrazide, X=OMe ( 1 ), H ( 2 ) NO₂ ( 3 )]. Detailed magnetic measurements reveal the presence of weak antiferromagnetic interactions between the Yb centers and a field-induced slow relaxation of magnetization in all complexes. A higher energy barrier for spin reversal was observed for complex 1 (U_eff=50 K) and it decreases in the order of 2 (47 K) to 3 (40 K). Notably, complex 1 shows a remarkable energy barrier within the frequency range of 1–850 Hz reported for Yb-based SMMs. Further, ab initio calculations show a higher axial anisotropy and lower quantum tunneling of magnetization (QTM) in the ground state for 1 compared to 2 and 3 . It was also observed that the presence of a strong crystal field in the equatorial plane (when the ∡ O1−Yb−O3 bond angle is close to 90°) enhances the axial anisotropy and improves the SMM behavior in the studied complexes. Both the experimental and theoretical analysis of relaxation dynamics discloses that Raman and QTM play major role on slow relaxation process for all complexes. To provide more insight into the exchange interactions, broken-symmetry DFT calculations were performed.     

Double Humped Grey and Black Solitons in Kerr Nonlinear Media

The existence of a new class of double humped grey and dark solitons in a Kerr nonlinear medium has been predicted in this paper. Following well known variational procedure, the dynamics of the propagating soliton has been converted to a Hamiltonian formulation. A set of ordinary differential equations is then derived, which was subsequently examined to predict the existence of double humped grey and dark solitons. Linear stability analysis, numerical appreciation and phase plane dynamics show that these solitons are stable.