Donor-Type Nickel–Dithiolene Complexes Fused with Bulky Cycloalkane Substituents and Their Application in Molecular Conductors

The effects of substituents on the arrangement of metal–dithiolene complexes based on π-conjugated systems, which are extensively used to synthesize various functional materials, have not been studied adequately. New donor-type nickel–dithiolene complexes fused with bulky cycloalkane substituents [Ni(Cn-dddt)2] (C5-dddt = 4a,5,6,6a-pentahydro-1,4-benzodithiin-2,3-dithiolate; C6-dddt = 4a,5,6,7,8,8a-hexahydro-1,4-benzodithiin-2,3-dithiolate; C7-dddt = 4a,5,6,7,8,9,9a-heptahydro-1,4-benzodithiin-2,3-dithiolate; and C8-dddt = 4a,5,6,7,8,9,10,10a-octahydro-1,4-benzodithiin-2,3-dithiolate) were synthesized in this study. All the complexes were crystallized in cis-[Ni(cis-Cn-dddt)2] conformations with cis-oriented (R,S) conformations around the cycloalkylene groups in the neutral state. Unique molecular arrangements with a three-dimensional network, a one-dimensional column, and a helical molecular arrangement were formed in the crystals owing to the flexible cycloalkane moieties. New 2:1 cation radical crystals of [Ni(C5-dddt)2]2(X) (X = ClO4− or PF6−), obtained by electrochemical crystallization, exhibited semiconducting behaviors (ρrt = 0.8 Ω cm, Ea = 0.09 eV for the ClO4− crystal; 4.0 Ω cm, 0.13 eV for the PF6− crystal) under ambient pressure due to spin-singlet states between the dimers of the donor, which were in accordance with the conducting behaviors under hydrostatic pressure (ρrt = 0.2 Ω cm, Ea = 0.07 eV for the ClO4− crystal; 1.0 Ω cm, 0.12 eV for the PF6− crystal at 2.0 GPa).

Sulfate Assisted Synthesis of α-type Nickel Hydroxide Nanowires with 3D Reticulation for Energy Storage in Hybrid Supercapacitors

Nickel hydroxide, as a high high-efficiency electroactive material, is a promising electroactive material for advanced hybrid supercapacitors due to its high theoretical capacity, low-cost, good thermal and chemical stability. Although...

SYNTHEIS OF NI IMPREGNATED HYPERCROSSLINKED POLYSTERENE FOR CATALITIC HYDROGENATION OF D-GLUCOSE

Development of efficient catalysts is in focus of modern chemical technology for production of fine chemicals. D-sorbitol is widely used as sweetener, food additive and fuel compound is typically produced by D-glucose hydrogenation over Ni-Reney catalyst. However, this catalyst is characterized by not sufficient stability and selectivity to D-sorbitol formation. The described study is devoted to synthesis of nickel containing hypercrosslinked polystyrene for D-glucose hydrogenation process. Hypercrosslinked polystyrene is one of the representatives of crosslinked polymers with rigid matrix applicable for metal nanoparticles synthesis. However, hypercrosslinked polystyrene is characterized by high surface hydrophobicity that prevent impregnation of high amount of active metal over it surface. To overcome this disadvantage hypercrosslinked polystyrene was modified by hydrogen peroxide, chlorine and ammonia. A series of nickel based catalyst theoretically containing 25wt.% of nickel were synthesized. Modification of hypercrosslinked polystyrene results in appropriate increase in surface concentration of active metal. Synthesized Ni based catalysts were characterized by comparable Ni loading varying from 20.1 wt.% to 23.2 wt.%. Some increase in Ni loading can be subscribed to presence of surface-active groups in a case of modified hypercrosslinked polystyrene application. Mesopores surface area decrease from 126 m2/g to 69 m2/g in case of catalysts on modified hypercrosslinked polystyrene. Catalytic hydrogenation of D-glucose over synthesized Ni-containing catalysts showed considerable increase in turnover frequency (TOF) for all samples compare to commonly used Reney type nickel. Increase in TOF can be subscribed to appropriate increase of active metal surface concentration. Beside, some increase in catalyst selectivity to sorbitol took place. Considerable improvement of selectivity to sorbitol can be explained by increasing of desired D-glucose hydrogenation reaction rate, while reaction rate of D-glucose isomerization process to D-fructose remain the same. The achieved TOF for most active catalyst was found to be 0.27 s-1 and catalysts selectivity to D-sorbitol 98%.