Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes.
نویسندگان
چکیده
A series of [Ru(bpy)2(C^N)][PF6] (HC^N = 2-phenylpyridine derivative) complexes functionalized in the cyclometallating C^N phenyl ring with F, Me, OMe, CO2Me, S(t)Bu, SO2Me (ligands H1-H6) or in the C^N pyridine ring with 4-CO2Me or 4-C6H4P(O)(OEt)2 substituents (ligands H7 or H9) have been prepared and characterized; representative crystal structures confirm the structural features of the complexes. When the C^N ligand contains a CO2H substituent (ligand H28), deprotonation in addition to cyclometallation occurs to give a neutral, zwitter-ionic complex [Ru(bpy)2(8)]. The synthesis of the cationic complexes requires addition of a silver(i) salt (AgPF6 or AgBF4) to abstract Cl(-) from cis-[Ru(bpy)2Cl2] and (1)H NMR spectroscopic data are consistent with interactions between Ag(+) and the coordinated C^N ligand in [Ru(bpy)2(C^N)](+). The absorption spectra of [Ru(bpy)2(C^N)][PF6] (C^N = 1-6) are similar, but the introduction of the anchoring domains in [Ru(bpy)2(C^N)][PF6] with C^N = 7 or 9 enhances the absorption response; the greatest influence is observed in [Ru(bpy)2(9)](+) with the introduction of the 4-C6H4P(O)(OEt)2 substituent. Trends in emission and electrochemical behaviours of the complexes are interpreted in terms of the influence of the electronic properties of the C^N ligand substituents on the energies of the HOMO which is localized on the C^N ligand and Ru centre. This study provides an optimized synthetic route to the phosphonate ester derivative [Ru(bpy)2(9)][PF6], designed to anchor to a semiconductor surface; this complex also exhibits the most favourable absorption properties among the complexes studied.
منابع مشابه
Rapid energy transfer in bichromophoric tris-bipyridyl/cyclometallated ruthenium(II) complexes.
The synthesis, characterization, and photophysical properties of the N6-N5C bichromophoric [(bpy)2Ru(I)Ru(ttpy)][PF6]3 (bpy is 2,2'-bipyridine and ttpy is 4'-p-tolyl-2,2':6',2''-terpyridine) and [(bpy)2Ru(II)Ru(ttpy)][PF6]3 (I and II are bpy-dipyridylbenzene ditopic ligands bridged by an ethynyl and phenyl unit, respectively) complexes are reported together with the model mononuclear complexes ...
متن کاملCytotoxicity of cyclometallated ruthenium complexes: the role of ligand exchange on the activity.
The cyclometallated Ru(II) complexes cis-[Ru(phpy)(phen)(CH3CN)2](PF6) (1; phpy(-)=deprotonated 2-phenylpyridine, phen=1,10-phenanthroline) and cis-[Ru(phpy)(bpy)(CH3CN)2](PF6) (2; bpy=2,2'-bipyridine) were investigated as potential agents for photodynamic therapy. The presence of phpy(-) in the coordination sphere results in a red-shift of the Ru→phen and Ru→bpy metal-to-ligand charge transfer...
متن کاملTuning emission wavelength and redox properties through position of the substituent in iridium(III) cyclometallated complexes.
Cyclometallated phenyls with substituents para to the metal have a larger impact on the redox potentials and emission of complexes [Ir(R-ppz)(2)(bipy)][PF(6)] than substituents at the meta position and hence enable tuning of emission wavelength over a wider range using the same substituent.
متن کاملSynthesis, Characterization, Electrochemical and Spectroelectrochemical Properties of Ruthenium(II) Complexes Containing Phenylcyanamide Ligands and Effect of the Inner- Sphere on the Ru-NCN Chromophore
[Ru(terpy)(bpy)(L)]PF6 complexes, where terpy is 2,2΄:6′,2″– terpyridine, bpy is 2,2΄ - bipyridine and L is monoanions of 4 - bromophenylcyanamide (4 - Brpcyd), 4-methoxyphenylcyanamide (4 - MeOPcyd), 2, 4 - dibromophenylcyanamide (2,4 - Br2pcyd), 2,4-dimethylphenylcyanamide (2,4 - Me2pcyd), 2 - methylphenylcyanamide (2 ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Dalton transactions
دوره 44 4 شماره
صفحات -
تاریخ انتشار 2015