Structural Investigations of Oligomeric Axially Bridged Ruthenium Phthalocyanines by EXAFS Spectroscopy

Abstract

To obtain more information about the structure of phthalocyaninatoruthenium compounds an EXAFS investigation was carried out on amorphous bisaxially bridged phthalocyaninatoruthenium(II) oligomers, [PcRu(tz)]n (1), [PcRu(pyz)]n (2) and [PcRu(dib)]n (3). Detailed structural models for the three compounds were deduced from the determined atomic distances around the metal center. A bisaxial structure of the ligands could be proven for all compounds and additionally, the structure parameters could be determined.

Synthesis, Complexation, and Coordination Oligomerization of 1,8-Pyrazine-Capped 5,12-Dioxocyclams

“…Treatment of 2,6-dimethylpyrazine with a slight excess of N -bromosuccinimide under incandescent light with benzoyl peroxide as the initiator produced the dibrominated pyrazine 2 in 17% isolated yield. As is typical for reactions of this type,5e reaction efficiency is compromised by overbromination. Further, 2 is relatively unstable to the reaction conditions and even decomposes when pure on standing.…”

“…Over the past decade, coordination polymers have undergone development in a number of different directions. Major advances in the utilization of coordination polymerization for the self-assembly of supramolecular nanostructures have been made. − Many have host−guest properties and can act as synthetic receptors 4 or coordination complex analogues of zeolites . When the ligands bridging the metal centers can transmit electronic information, the resulting coordination polymers may have unusual optical, magnetic, or electronic properties, as well as the potential to recruit several metal centers to interact with a single substrate in a catalytic process.…”

“…When the ligands bridging the metal centers can transmit electronic information, the resulting coordination polymers may have unusual optical, magnetic, or electronic properties, as well as the potential to recruit several metal centers to interact with a single substrate in a catalytic process. This class of bridging ligands includes pyrazines, triazines and tetrazines, cyano and isocyano groups, and polyacetylene-linked bi- and terpyridines …”

Optical and Redox Properties of Ruthenium Phthalocyanine Complexes Tuned with Axial Ligand Substituents

“…We note that a mixture of four positional isomers is expected because of the arrangements of the t-butyl groups around the macrocycle. [34][35][36] No attempt was made to separate individual isomers. Unlike the analogous peripherally unsubstituted complex, [PcRu-(NH 3 ) 2 ], which is insoluble in most solvents, the tetra-tertbutyl-substituted complex is soluble in many organic solvents.…”

The innovative momentum of crystal engineering

“…It is trivial to mention that progress in designing the properties of microcrystalline and amorphous organic conductors turned out to be much more difficult. 19 However, Saalbeck has shown how to engineer specifically non-crystalline solids by linking two aromatic building blocks with a spiro-carbon centre. 20 Amorphous compounds like the hole transport material spiro-TAD exhibit high glass transition temperatures.…”