Ruthenium complex polymers structures

The polymers are synthesized by utilizing the Heck coupling reaction. Their structures are shown as polymers V to VII (Scheme 6). The metal-to-ligand charge transfer of the ruthenium complexes of polymer VI results in... 

Figure 5.61 Schematic representation of a [Ru(bpy)3]2+/a-ZrP viologen structure on silica, plus the sequence of fast (1,2) and slow (3) electron transfer steps that follow photoexcitation of the photoactive ruthenium-containing polymer MDESA, p-methoxyaniline diethylsulfonate. Reprinted from Coord. Chem. Rev., 185-186, D. M. Kaschak, S. A. Johnson, C. C. Waraksa, J. Pogue and T. E. Mallouk, Artificial photosynthesis in lamellar assemblies of metal poly(pyridyl) complexes and metalloporphyrins, 403-416, Copyright (1999), with permission from Elsevier Science...

Polymerization of methyl methacrylate (MMA) and styrene in bulk via ruthenacarboranes and carbon tetrachloride was investigated first, ft was found that proposed ruthenium complexes were able to efficiently catalyze polymerization of MMA in conjunction with carbon tetrachloride as an initiator. Moreover, as follows from the data obtained (Table I), high conversion of the monomer is achieved in a number of cases. The structure of ruthenium carborane complexes closo or exo-nido) has a substantial effect on the kinetic parameters of MMA and styrene polymerization, as well as on the molecular-weight characteristics of synthesized polymers. 

The occurrence of piezoelectric behaviour in LB films has been known for some time [57,58], and a 30 X-type layer LB film of (37) was found to give opposite signs of the piezoelectric strain coefficients d i and d [59], the latter having a value of 1.5 pC which is approximately an order of magnitude lower than that of the well-documented polymer poly(vinylidene fluoride) (PVDF). Values for 31 of 0.023 and 0.170 pC N have also been obtained for alternate-layer structures of 22-tricosenoic acid with docosylamine, and a ruthenium complex with docosanoic acid respectively [60]. As the use of pyroelectric materials in detector applications requires that the materials possess only low levels of piezoelectricity (high levels introduce problems of microphony), this suggests that the former materials would be better suited for pyroelectric detector applications, while the latter system would be more appropriate for piezoelectric-based applications. 

Polyamides and polyesters containing ruthenimn bipyridine complexes in their structures have been synthesized by Chan and coworkers." " Scheme 14 depicts the synthesis of polymer 64 by reaction of the metal-containing dicarboxylic acid complex 61 and the organic dicarboxylic acid (62) with an aromatic or aliphatic diamine (63). These polymers were thermally stable to temperatures between 320 and 500°C. Many of the polymers exhibited liquid crystalline characteristics. The photoconductivity of this class of polymer increased with increasing metal content." Chan also reported that polybenzo-bw-oxazoles and polybenzo-Z>w-thiazoles that contain ruthenium complexes coordinated to 2,2 bipyridyl units in the backbone... 

The results presented here seem to indicate that 1) the local order about ruthenium centers in the polymers is essentially unchanged from that in the monomer complex and 2) that the interaction with the electrode surface occurs without appreciable electronic and structural change. This spectroscopic information corroborates previous electrochemical results which showed that redox properties (e.g. as measured by formal potentials) of dissolved species could be transferred from solution to the electrode surface by electrodepositions as polymer films on the electrode. Furthermore, it is apparent that the initiation of polymerization at these surfaces (i.e. growth of up to one monolayer of polymer) involves no gross structural change. 

The chemical structure of the polymers was confirmed by NMR and elemental analysis, and spectroscopically characterized in comparison with monodisperse low molecular weight model compounds. Scheme 5 outlines the approach to the model compounds. Model compounds 31-34 were synthesized by complexation of the ruthenium-free model ligands 29/30 with 3/4. The model ligands were synthesized in toluene/diisopropylamine, in a similar fashion as the polycondensation using Pd(PPh3)4 and Cul as catalyst (Sonogashira reaction) [34,47-49]. 

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