Synthesis of a new polypyridinic highly conjugated ligand with electron-acceptor properties

A new acceptor polypyridinic ligand functionalized with a quinone fragment is reported. The ligand, dipyrido[3,2-a:2′,3′-c]-benzo[3,4]-phenazine-11,16-quinone, Nqphen, was synthesized by condensation of 1,10-phenanthroline-5,6-dione and 2,3-diamino-1,4-naphthoquinone. The syntheses of two rhenium complexes with this ligand are also reported

Synthesis and characterization of rhenium(I) complexes with the polypyridinic quinone functionalized electron acceptor ligand [3,2-a:2′,3′-c]-benzo[3,4]-phenazine-11,16-quinone, Nqphen

In this work, the synthesis and characterization of fac-[Re(CO) 3(Nqphen)(L)]PF6 complexes is reported. Nqphen is the quinone substituted acceptor ligand [3,2-a:2′,3′-c]-benzo[3,4]- phenazine-11,16-quinone, and L represents the donor monodentate pyridine substituted ligands 4-tert-butylpyridine (t-Bupy), 4-methoxypyridine (MeO-py) or 10-(4-picolyl)phenothiazine (py-PTZ). The complexes were synthesized by refluxing in methanol the metal precursor fac-Re(CO)3(Nqphen)TfO (TfO = trifluoromethanesulphonate anion) with the corresponding L ligand. The UV-Vis spectra of the complexes are dominated by intense intraligand (IL) bands, and less intense metal ligand charge transfer (MLCT) bands with maxima in the 380-400 nm region. The IR shows the typical pattern for tricarbonyl Re complexes with facial (fac) geometry. An additional v(CO) stretching band, attributed to the quinone fragment of Nqphen, is observed. Electrochemical data indicate that the acceptor capacity of Nqphen is increased in the complexes with regard to the free ligand. This effect is sensitive to the nature of the L ligand, following the order: MeO-py < t-Bupy < py-PTZ, indicating therefore that the donor capacity of L affects the rest of the molecule. The results obtained for the fac-[Re (CO)3(Nqphen)(pyPTZ)]PF6 complex here reported were compared with those observed for the homologous complex fac-[Re(CO) 3(Aqphen)(L)]0/+, with Aqphen = 12,17-dihydronaphtho[2,3- h]dipyrido[3,2-a:2′,3′-c]-phenazine-12,17-dione, and L = Cl -, TfO-, py-PTZ. © 2010 Elsevier Ltd. All rights reserved

Synthesis and characterization of polypiridine-based rhenium(I) complexes with pyrazino[2,3-f][1,10]phenanthroline

A series of tricarbonyl rhenium(I) complexes of the type fac-[Re 1(CO)3(Ppl)(L)]0/+, where ppl is pyrazino[2,3-f][1,10]phenanthroline, and where L is Cl-, TIO -, 4-(tert-butyl)pyridine (tBu-py), 4-methoxypyridine (MeO-py), 4,4′-bipyridyl (bpy), or 10-(picolin-4-yl)phenothiazine (pptz), were synthesized and fully characterized. In all complexes, an increment in the electron-acceptor properties of ppl compared to the free ligand was observed. This effect was more significant for pyridine-type ligands, especially for pptz, compared to Cl- or TfO-. The properties of fac-[Re(CO)3(ppl)(pptz)]PF6 were compared with those of the analogous compound fac-[Re(CO)3(dppz)(pptz)]PF6, where dppz is dipyrido(3,2-a: 2′,3′-c)phenazine, the goal being to generate long-lived excited charge-transfer (CT) states. In this respect, fac-[Re(CO)3(ppl)(pptz)]PF6 seems to be a promising candidate

Influence of ligand structure and molecular geometry on the properties of d6 polypyridinic transition metal complexes

Different strategies to improve the excited state properties of polypyridinic complexes by varying ligand structure and molecular geometry are described. Bidentate and tetradentate ligands based on fragments as dipyrido[3,2-a:2′,3′-c]phenazine, dppz, and pyrazino[2,3-f][1,10]-phenanthroline, ppl, have been used. Quinonic residues were fused to these basic units to improve acceptor properties. Photophysical studies were performed in order to test theoretical predictions