Diazaporphyrins: synthesis, characterization and X-ray crystal structure of (3,7,13,17-tetramethyl-2,8,12,18-tetrabutyl-5,15-diazaporphinato)chloroindium(III)

Synthesis and Study of the Binuclear μ‐Oxodiiron(III) Complexes of 5‐Monoaza‐ and 5,15‐Diaza‐Substituted β‐Octaalkylporphyrins

“…[35,41,42] The spectral changes observed upon acidification of the μ-O(FeAP) The UV/Vis spectra of the resulting acido complexes (X)FeAP are very characteristic; instead of the Q-bands of the initial μ-O(FeAP) 2 at 595-610 nm (Figure 9, a,d), the new broad absorption bands appear at 540-570 and 640-670 nm (Figure 9, b,e). These also differ greatly from the typical spectra of meso-azaporphyrin complexes with M II and M III metals, for example, CuAP, [41,42] ZnAP [39] and (Cl)InAP, [31,35] which contain the intense and sharp Q-band in the visible region ( Figure 9, c,f). Analogous spectra were previously reported for the corresponding chloride complexes of Fe III octaethylmonoazaporphyrin, (Cl)FeMAPEt 8 , [17] and Fe III diazaporphyrin, (Cl)FeDAP.…”

“…The resonance signals in the 1 H NMR spectra of μ-oxo complexes μ-O(FeMAP) 2 ( Figure 6) and μ-O(FeDAP) 2 (Figure 7, A) are considerably broadened and shifted compared with the sharp signals in the corresponding free bases (see Table 3) or diamagnetic complexes (e.g., with In III [31,35] ). A downfield shift is observed for the resonances of the protons in the α-positions of alkyl groups; the signals of α-CH 3 protons shift from δ = 3.5-3.6 to 5.3-6.0 ppm.…”

“…[39,40] For the binuclear μ-oxo complexes, the Q-band is broadened and the maximum [596 nm for μ-O(FeMAP) 2 and 608 nm for μ-O(FeDAP) 2 ] is bathochromically shifted compared with the mononuclear complexes; the maximum of the Q-band is www.eurjic.orgobserved at 565-580 nm for the Cu II and In III complexes of meso-monoaza-substituted porphyrins, CuMAP and (Cl)-InMAP, [35,41] and at 580-595 nm for the meso-diaza-substituted species CuDAP and (Cl)InDAP. [31,42] The Soret band maximum in μ-O(FeMAP) 2 (351 nm) and μ-O(FeDAP) 2 (362 nm) is shifted hypsochromically (385-400 and 375-385 nm in the mononuclear complexes of MAP and DAP, respectively), and has a distinct long-wave shoulder. Such spectral peculiarities observed for μ-O(FeAP) 2 might be due to the exciton interaction of two closely located π-chromophores in the binuclear μ-oxo complexes.…”

Study of acid-base interactions of mono- and diazaporphyrin indium complexes with acetic and trifluoroacetic acids by 1H NMR and electronic spectroscopy

“…

Indium complex of 13,3,7,8,12,InMAP was synthesized, and acid3base interactions of the meso-nitrogen atoms in (Cl)InMAP and its diaza analog (Cl)InDAP with acetic and trifluoroacetic acids were studied by 1 H NMR and electronic spectroscopy. Depending on the medium, the complexes and proton-donor species HA give rise to acid solvates >N...(HA) n which are converted to final acid3base interaction products, H-complexes >N...H+...A 3 (HA) m or ionic associates >NH + ...A 3 (HA) l , as the acidity of the medium rises.

…”

“…The appearance of the above properties is determined by the nature of both macrocyclic and axial ligands. We recently synthesized indium complex with 2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphyrin (Cl)InDAP and examined its structure by X-ray diffraction [3]. We also prepared a series of five-coordinate In(III) complexes including octaphenyltetraazaporphyrin and some unidentate anionic ligands (X)InTAP (X = F, Cl, NCS, NCO) [4].…”