Synthesis and Properties of (Phthalocyaninato)ruthenium(II) with Bisaxially Coordinated Azanaphthalenes

Abstract

(Phthalocyaninato)ruthenium(II) (PcRu) reacts with different azanaphthalenes such as quinoxaline, 2-methylquinoxaline, quinazoline, phthalazine, quinoline, pyrido [2,3-b]pyrazine, cussed in detail for all the complexes prepared. pteridine, isoquinoline and 1,5-naphthyridine to form the corresponding bisaxially coordinated PcRuL, complexes 1 -9. The IR, 'H-NMR, UV/Vis, TG/DTA, and FD-MS data are disBisaxially coordinated macrocyclic transition-metal complexes MacMLz and bridged systems [MacM(L)], with phthalocyanine (Pc), tetrabenzoporphyrin (TBP), or 1,2-and 2,3-naphthalocyanine (1,2-, 2,3-Nc) as the macrocycle (Mac), transition metals, e.g. iron, ruthenium, and cobalt as the central metal atom (M), and ligands (L) like pyrazine (pyz), tetrazine (tz), diisocyanobenzene (dib), etc. have been systematically investigated by us regarding their semiconducting properties','). The semiconducting behavior of the bridged systems [MacM(L)], as well as other properties, e.g. solubility of the monomers MacMLt in organic solvents, do not only depend on the macrocycle Mac, but also on the nature of the ligands L3).For the synthesis of bisaxially coordinated transitionmetal complexes MacMLz and [MacM(L)], till now only monocyclic ligands of the type mentioned above have been used. It is expected, that structually different ligands containing a more extended x system, could lead to different physical properties of the corresponding complexes, e.g. to higher solubilities in organic solvents or to lower oxidation potentials.In this report, we describe for the first time the synthesis and properties of the azanaphthalene-coordinated (phthalocyaninato)ruthenium(II) complexes 1 -9. Results and DiscussionSynthesis of (Phthalocyaninato)ruthenium(lI) Complexes 1 -9

Thin films of a dimeric ruthenium phthalocyanine complex on gold

“…Complex 1 also has a broad low intensity absorption band centred at 426 nm. Similar absorption bands have previously been observed in the electronic spectra of [PcRuL 2 ] complexes where L = (2-oxopropyl)pyridine-4-carboxylate [13] or pyrazine [21] and are attributed to metalto-ligand charge-transfer (MLCT). The spectrum of the dimeric complex 2 is also dominated by the Q-and Soret bands and the molar absorptivities of these bands are greatly increased relative to the monomeric complexes due to the two phthalocyanine rings per molecule.…”

Synthesis, electrochemistry and spectroscopic properties of ruthenium phthalocyanine and naphthalocyanine complexes with triphenylarsine ligands

“…Signals arising from protons "e", furthest from the ruthenium metal centre, are observed at δ 7.87. The macrocyclic protons, in particular "a" and "b", where the influence of the axial ligands is greatest, are shifted upfield compared to analogous complexes bearing aromatic N-heterocyclic axial ligands [16,29,30] such as pyridine and quinoline. This trend is also observed in the spectrum of 1 and indicates that the AsPh 3 ligand is more electron donating than the N-heterocyclic ligands.…”

“…In contrast, the coordinated ligand displays three distinct resonances significantly shifted upfield at δ 4.59, 6.32, and 6.69 ( Figure 2). The ortho-phenyl protons will experience the greatest shielding due to macrocyclic diamagnetic ring currents [18,27,29] and thus the signal at δ 4.59 is assigned to the twelve ortho-protons of the coordinated ligands. The signals at δ 6.32 and 6.69 are assigned to the meta-and para-phenyl protons, respectively.…”

Synthesis, Characterization, Electrochemistry, and Spectroscopic Properties of Some Anthracenyl Functionalized Phthalocyanine Complexes of Ruthenium(II)

“…The electronic spectra of ruthenium phthalocyanines (C 1 R RuPc), (C 2 R RuPc), and (C 3 R RuPc) show the Q bands of a typical macrocycle substituted Pc [24][25][26]. The energy level location corresponding to this band is illustrated in (Figure 1).…”

“…In the UV-region, anthracene displays strong absorptions between 300 and 400 nm in the solution, with pronounced vibronic peaks at 331, 350, 369, and 388 nm characteristic of anthracene derivatives and with highest molar absorptivity coefficient recorded for C 1 R RuPc [27]. The presence of these bands is thought to have overlapped the weak Soret band which normally appears in the region 340-385 nm and attributed to a charge transfer (CT) transition [4,25,26]. In the visible region, (C 1 R RuPc) and (C 2 R RuPc) showed single-broad Q-bands (633, 618 nm) with accompanied weak shoulder bands at 573 and 566 nm, respectively.…”