Ruthenium complexes 2,2 ,2”-Terpyridyl

Upon excitation of the metal complex centre, triplet energy transfer to the donor appended porphyrin rapidly quenches the excited state of the central ruthenium bis-terpyridyl unit, whereas excitation of the gold porphyrin, leads in less than 1 ps to the triplet-excited state [23], which is unreactive to-... 

Aspley CJ, Williams JAG (2001) Palladium-catalysed cross-coupling reactions of ruthenium bis-terpyridyl complexes strategies for the incorporation and exploitation of boronic acid functionality. New J Chem 25 1136... 

Figure 14. Kb values, from intervalence measurements, on a log scale, as a function of the through-space metal-metal distance +, ruthenium bipyridylpolyene complexes (series 1) , ruthenium bis(terpyridyl) complexes (series 2) , ruthenium bis(cyclometallated) complexes, dipyridylbenzene family (series 3) , ruthenium bis(cyclometallated) complexes, phenylpyridine family (series 4) A, bis(ferrocenyl)polyenes (series 5). Additional measurements a, bis(cyclometallated) complexes, phenylpyridine family with diethynylanthracene as spacer b, bis(ferrocene) with three phenylene and four vinylene units as spacer c, bis[ruthenium(trisbipyridyl)] with five double bonds as spacer. Note that the Cp (dppe)Fe system bridged by octatetrayne (13 A, 0.32 eV) is outside the graph.

In early work in 1995, just before the concept of dynamic combinatorial chemistry was first explicitly recognized, Hamilton et al. screened a combinatorial library of ruthenium A(terpyridyl) complexes.From five differently substituted terpyridine ligands, a series of 15 different coordination complexes was synthesized and isolated. The library was screened for affinity for dicarboxylate or diammonium guests using microcalorimetry or picrate extraction, and several receptors were identified (Fig. 2). 

The X-ray structure of zinc naphthalocyanate has been determined with Zn—N bond lengths of 1.983(4) A.829 Pentanuclear complexes with a zinc phthalocyanine core and four ruthenium subunits linked via a terpyridyl ligand demonstrate interaction between the photoactive and the redox active components of the molecule. The absorbance and fluorescence spectra showed considerable variation with the ruthenium subunits in place.830 Tetra-t-butylphthalocyaninato zinc coordinated by nitroxide radicals form excited-state phthalocyanine complexes and have been studied by time-resolved electron paramagnetic resonance.831... 

The spherical dendrimer 62 serves as example of the metal-linked type. While both the central core (incorporating twelve terpyridine sites) and the terpyridine-containing components on the periphery of the structure are obtained by conventional organic synthesis, the overall dodeca-ruthenium structure assembles in 75% yield on reaction of the core with 15 equivalents of the 1 1 rathenium(III) chloride complex of the terminating terpyridyl derivative. 

The terdentate ligand terpyridyl affords a range of complexes fusion of RuCla with terpy gives Ru(terpy) , while refluxing RuClj with an ethanolic solution of the ligand yields RuCl3(terpy). Both of these are doubtless 6-coordinate. Ruthenium bis(terpyridine) complexes are also attracting attention as photosensitizers [76]. 

Polypyridyl transition metal complexes, especially those of ruthenium(II), have been extensively apphed in light harvesting and information storage, because they exhibit a wide range of photophysical and electrochemical properties. Storrier et al. have reported the synthesis and characterization of PAMAM dendrimers functionalized with tris(bipyridyl) ruthenium(II) (dend- -[Ru(bpy)3] +) or bis (terpyridyl) ruthe-nium(II) (dend-n-[Ru(tpy)2] ) complexes (GO, 1, 2, 3, and 4 with 4, 8, 16, 32,... 

The presence of two terpyridyl groups in 41c provides opportunities to form dinuclear ruthenium(II) bis(terpyridine) complexes 44a and 44b bearing helical... 

Hosts with metals as structural elements may be further divided into inert and labile coordination complexes. In the former case, the metal-ligand bonds are long-lived on the human time scale and the host compound binds anions as a unit in exactly the same way as non-metal-containing analogues. For example, in compound 2.85, two thiourea-derived terpyridyl ligands are held together in a well-defined way by a relatively inert (low-spin d ) ruthenium(ii) centre (Scheme 2.12). The host binds long dicarboxylates, particularly pimelate. ... 

The development of polynuclear ruthenium(II) terpyridine molecular wire molecules based on the biferrocene building block bfc were recently reported by Dong et al. [91]. The multinuclear supramolecules assembled from r,r -bis(terpyridyl) biferrocene redox-active sub-units attached to Ru(II) ions were prepared by, for example, the reaction of bfc-terpy (133) and bfc(terpy)2 (134), respectively, with LRuCls (L = terpy, fc-terpy), LRuCl2(dmso) (L = bfc-terpy, dmso = dimethylsulfoxide) or RuCl2(dmso) in the appropriate ratios as outlined in Figure 11 [91], Complexes Ru(bifc-terpy)(dmso)Cl2 (135), [Ru(terpy)(bifc-terpy)](PFg)2... 

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