Photochemical and thermal synthesis and characterization of polypyridine ruthenium(ii) complexes containing different monodentate ligandsElectronic supplementary information (ESI) available: View of the dimeric units of 8 and proton indexation used in the 1H NMR data. See http://www.rsc.org/suppdata/dt/b3/b310198c/

Abstract

The photochemical and thermal synthesis of a series of [Ru(tpy)(phen)L] 2ϩ complexes where terpy = 2,2Ј:6Ј,2Љterpyridine (terpy) or 4-(3,5-di-tert-butyl)phenyl-2,2Ј;6Ј,2Љ-terpyridine (terpy*), phen = 1,10-phenanthroline and L monodentate ligands such as Cl Ϫ , NC Ϫ , CH 3 CN, pyridine, isoquinoline (iq), 4-dimethylaminopyridine (dmap), 4-(4Ј-methylpyridinium)pyridine (mqt), phenothiazine (ptz), 3,5-lutidine(lut) and H 2 O are described. The complexes have been characterized by 1 H (COSY and ROESY) NMR spectroscopy, mass spectrometry (FAB and ES-MS), cyclic voltammetry, UV-vis absorption and emission spectroscopy and single-crystal X-ray diffraction. Photochemical experiments have shown that the ligands L can be photochemically expelled and replaced by CH 3 CN molecules used as solvent. This type of ligand interchange occurs efficiently and very selectively. The reaction has the potential to be applied to a wide range of entering ligands (thioethers, ethers, pyridines, sulfoxides, nitriles, amides) and indicates the high stability of the Ru(terpy)(phen) core under the irradiation conditions.

Synthesis and structural characterization of some polypyridyl and polypyrazolyl Ru(II) complexes

“…The bond lengths and angles are within the range found for similar structures described in the literature. [48][49][50][51][55][56][57][58][59][60][61][62][63] In structures 13 and 14, the shortest Ru-N bond length is the Ru-N bond to the central pyridine ring in ttp ligand. The Ru-N bond distances in bpy ligands which are trans to the monodentate ligands (Cl or bpe) are shorter than those in the other pyridine rings in bpy ligands.…”

Transition‐Metal‐Complexed Molecular Machine Prototypes

“…The syntheses of complexes of the type Ru(terpy)(phen)(L) 2+ have been described for a great variety of ligands L (chloride, water, acetonitrile, benzonitrile derivatives, pyridines substituted in 3,4 and/or 5 positions, sulfoxides, and thioethers). [22,23] The absorption maxima of these complexes vary with the nature of the monodentate ligands, from ca. 430 nm for sulfoxides to ca.…”

“…12). [22] In Ru(terpy)(phen)(L) 2+ complexes, the monodentate nature of the leaving ligand L and the less-crowded coordination sphere around the ruthenium center compared to Ru(diimine) 3…”

N‐Acetylmethionine and Biotin as Photocleavable Protective Groups for Ruthenium Polypyridyl Complexes

“…Meanwhile, the UV/Vis spectra of [3] 2 + and [4] 2 + in water show metal-toligand charge transfer (MLCT) bands in the visible region characterized by absorption maxima at 452 and 444 nm, respectively (see the Supporting Information, Figure S5), which is consistent with thioether-bound ruthenium complexes. [29] Finally, both compounds show only one darkorange spot, observed by TLC on silica gel. Thus, the presence of the two close A6 doublets for complex [3] 2 + can be explained by considering the chirality of N-acetyl-l-methionine.…”

“…[24,25] Secondly, unlike nitrogen-based ligands, thioethers are only weakly basic in water, which might make their ruthenium complexes less sensitive to pH changes. Finally, visible-light irradiation leads to the controlled release of thioether ligands, [26][27][28][29] which feature might be used to deliver locally the cytotoxic form of the ruthenium complex at the desired location ( Figure 1, route 2). The use of light to cure cancer, which has notably led to the clinical development of photodynamic therapy, [30][31][32] has also been proposed as an interesting development in metal-based anticancer drug research, in which the presence of oxygen is not required.…”