Synthesis, characterization, and electrocatalytic and electrical properties of novel ball-type four cyclopentyldisilanoxy-POSS bridged metallophthalocyanines

Abstract

The novel ball-type four cyclopentyldisilanoxy-POSS bridged binuclear metallophthalocyanines 4-6 (M = Zn, Co, Cu) were synthesized from the corresponding phthalodinitrile derivative 3 which can be obtained from the reaction of cyclopentyldisilanol-POSS 1 with 4-nitrophthalonitrile 2 in THF in the presence of K(2)CO(3) as the base by nucleophilic substitution of an activated nitro group in an aromatic ring. The structures of the target compounds have been characterized by elemental analysis, UV-Vis, IR, MALDI-TOF mass and (1)H-NMR spectroscopy techniques. The catalytic activity of the 5-based catalyst towards oxygen reduction in a fuel cell-similar medium involving carbon support and Nafion was observed to be superior when compared to those of 4-and 6-based catalysts, suggesting clearly that the presence of two cofacial redox-active metal centres in the ball-type structure increases the oxygen binding capability of the metal centre and the tendency for the formation of mu-peroxo species. The effect of heat treatment on the dc electrical conductivity and the impedance spectra of the films of 4 and 5 were also studied. The results showed that there were no considerable effects of heat treatment on the dc conductivity of the film of 4. On the other hand, after the films of 5 were annealed at 448 K in vacuum, the conductivity of the films increased approximately 10(3) times.

MALDI‐TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in

“…Since 2005 many other systems have been investigated. These include, but are not limited to, porphyrins and phthalocyanines,26–37 other nitrogen heterocycles,26, 38–46 other nitrogen ligands,47–53 metallocenes/aryl ligands,26, 54–60 phosphorus ligands,26, 44, 57, 59, 61–63 hydrazones,64 carboxylates,51, 54, 65 thiophenes,66, 67 acetylacetonates,59, 68 ethers,69, 70 polyynes/cumulenes,71 acetohydrazides,72 octreotate,73 tripsalen,74 thiols75 and quinolates 76. Successfully characterised compounds have contained, but are not limited to, magnesium,37 the first‐row transition metals in general,63, 68 specifically vanadium,59 chromium,74 manganese,28, 74 iron,26, 35, 40, 54, 59, 60, 63, 66, 74 cobalt,28, 29, 31, 33, 34, 40, 42, 64, 72 nickel,29, 33, 40, 64, 67, 72 copper,26, 29, 31, 33, 34, 39, 52, 64, 71, 72 zinc,26, 28, 29, 31–34, 40, 45, 48, 55, …”

“…Successfully characterised compounds have contained, but are not limited to, magnesium,37 the first‐row transition metals in general,63, 68 specifically vanadium,59 chromium,74 manganese,28, 74 iron,26, 35, 40, 54, 59, 60, 63, 66, 74 cobalt,28, 29, 31, 33, 34, 40, 42, 64, 72 nickel,29, 33, 40, 64, 67, 72 copper,26, 29, 31, 33, 34, 39, 52, 64, 71, 72 zinc,26, 28, 29, 31–34, 40, 45, 48, 55, 64, 65, 72 gallium,26, 42 the Group 4 metals,58 ruthenium,26, 44, 46, 53, 57, 73 rhodium,26 palladium,28, 41, 49, 50, 53, 55, 61–63, 67 silver,28, 29, 52, 71 cadmium,40, 43, 47, 72 indium,42 tin,38, 51, 54, 69, 70 rhenium,26 osmium,26 iridium,39, …”

History, development, and a new concept of phthalocyanines in Turkey

“…This promotes the interaction with oxygen molecules, likely the O-O bond breakage and thus reduction to water. 71 Detailed comparison and interpretation of the results included the activity of a platinum-based catalyst, which is the best at the present time due to its high catalytic activity and long-time stability in the full cell field although it is very expensive. Regarding RDE measurements, the catalytic activity of the ball-type Co 2 Pc 2 (Scheme 4) was observed to be superior when compared to those of ball-type Zn and Cu Pc and mono Pc of the same starting material, implying that the presence of 2 co-facial redox-active cobalt centers in the ball-type structure promotes the interaction with oxygen molecules and the tendency for the formation of µ -peroxo species and thus reduction to water.…”

Synthesis and Characterization of Phthalocyaninatosilicon With Bridging Ligands (L) (L = Dimethylsilane, Diphenylsilane, Methylphenylsilane)

“…Organic conductors based on organometallic compounds have been very important continuously, and new types of low‐dimensional polymeric compounds, most containing metallomacrocycles, have been synthesized and investigated . Metallomacrocycles such as metallophthalocyanines (PcMs) and metallonaphthalocyanines (NcMs), besides their many other possible applications such as dyes, catalysts, pigments, etc., have recently been intensively investigated in the area of their electrical conductivity, as part of the efforts to construct new types of bridging ligand metallomacrocyclic compounds …”