Ruthenium(II) Dipyridoquinoxaline-Norbornene:  Synthesis, Properties, Crystal Structure, and Use as a ROMP Monomer

Abstract

The synthesis, X-ray structure, and electrochemical and photophysical characterization of [Ru(phen)(2)dpq-n][PF(6)](2) (phen = phenanthroline, dpq-n = dipyridoquinoxaline-norbornene) are described. This complex contains a Ru(phen)(3)(2+) moiety in close conjugation with a norbornene unit and is the first example of a Ru(II) diimine complex capable of undergoing ring-opening metathesis polymerization. Luminescence studies of this complex showed an increase in quantum efficiency in polar solvents and in water. Preliminary ring-opening metathesis polymerization studies, carried out at low monomer-to-initiator ratio, showed the formation of an oligomeric mixture composed mainly of the dimer of this complex. This dimer exhibits photophysical and redox properties similar to those of the monomer, indicating that the Ru(phen)(3)(2+) moiety remains intact during the polymerization.

Metal–Ligand‐Containing Polymers: Terpyridine as the Supramolecular Unit

“…The inherent viscosity of the copolymer solutions decreased with the complexation with Fe(II) suggesting polymer chain shrinkage. In recent years, Fraser and coworkers, [35][36][37][38][39][40] Schubert and co-workers, [8,[41][42][43][44][45][46][47][48][49][50][51] Sleiman and co-workers, [52][53][54] Calzai and Tew [55] ,and Weck and co-workers, [56][57][58][59][60] among others have became interested in more precise polymer architectures by employing controlled polymerization techniques (see Figure 4). Their focus has been on the noncovalent functionalization with metal complexes and hydrogen bonding to achieve multistep and orthogonal self-assembly.…”

A Novel 1:1 Co-Crystal of Bis(1,10-Phenanthroline)(1,10-Phenanthroline-5,6-Dione)Nickel(II) Hexafluorophosphate and Tris(1,10-Phenanthroline)Nickel(II) Hexafluorophosphate Complexes, [Ni(phen)2(phen-dione)] [Ni(phen)3] (PF6)4

“…Our research into 1,10-phenanthroline-5,6-dione complexes [22][23][24][25] has led us to co-crystallization reaction of polypyridyl Ni(II) complexes with this ligand. 1,10-Phenanthroline-5,6-dione plays an important role as molecular scaffolding for supramolecular assemblies, building block for the synthesis of metallo-dendrimers, thin films of luminescent complexes and ligand for synthesis of ringopening metathesis polymerization monomer [26][27][28].…”

Desenvolvimento de materiais híbridos oriundos de óleos vegetais, olefinas cíclicas e centros de rutênio

“…As reações de ROMP apresentam uma série de vantagens na modelagem de polímeros insaturados funcionais em um arranjo bem definido [52][53][54][55][56][57][58] , proporcionando a síntese de polímeros contendo substituintes com metais de transição que podem ser ativos fotoquimicamente. Assim, pretende-se desenvolver moléculas que apresentem grupos cromóforos que possam ser direcionados para construção de uma única rede molecular.…”