Synthesis, Structure, and Spectroscopic and Electrochemical Properties of Heteroleptic Bis(phthalocyaninato) Rare Earth Complexes with a C₄ Symmetry

Abstract

4 } in refluxing octanol. The whole series of double-decker complexes 1 ± 11 were characterized by elemental analysis and various spectroscopic methods. The molecular structures of the Sm, Eu, and Er complexes 1, 2, and 8, respectively, were also determined by single-crystal X-ray diffraction analysis. The effects of the rare earth ion size on the reaction yield, molecular structure, and spectroscopic and electrochemical properties of these complexes were systematically examined.

Methyloxy Substituted Heteroleptic Bis(phthalocyaninato) Yttrium Complexes: Density Functional Calculations

“…[13] The calculated absorptions of 3 at 596, 660, 900, and 1497 nm also correspond well with the experimental data of Y(Pc)[PcA C H T U N G T R E N N U N G (b-OC 5 H 11 ) 8 ] (604, 668, 916, and 1549 nm, respectively). [14] However, in line with previous findings, [28] this method is not very successful in the high energy region.…”

“…(Table 2), [13,14] and this indicates that the TDDFT method can reasonably reproduce the electronic absorption spectra of phthalocyanine compounds in the long-wavelength region. The three strong absorptions of Y(Pc)[PcA C H T U N G T R E N N U N G (a-OC 5 H 11 ) 4 ] at 621, 652, and 691 nm have been assigned as the three split Q bands due to lowering of the molecular symmetry, [13] which should correspond with our calculated absorptions of 1 at 607 (V), 661 (III), and 680 nm (IV), respectively. However, the calculated band at 661 nm (III) was revealed to be electron-transfer band from Pc B to Pc A.…”

“…The fact that band III disappears in the absorption spectra of reduced bis(phthalocyaninato) rare earth metal double-decker complexes seems to support this theoretical assignment that band III is an electron-transfer band due to electronic transition involving the hole (b LUMO). The calculated absorption of 1 at 919 nm (II) corresponds well with the weak absorption of Y(Pc)[PcA C H T U N G T R E N N U N G (a-OC 5 H 11 ) 4 ] at 931 nm, [13] which was previously assigned as one of the two p radical anion bands. However, our TDDFT calculations show that this absorption (II) has almost no contribution from electronic transitions involving the hole (b LUMO).…”

Porphyrin‐Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties

“…[13] The porphyrincontaining phthalonitriles 2, 3, and 6 were then subjected to a one-pot mixed cyclization with unsubstituted phthalonitrile and with [Eu III A C H T U N G T R E N N U N G (acac)(Pc)] as the template in the presence of DBU in refluxing n-pentanol. [14,15] As expected, these reactions led to the formation of a mixture of cyclized products from which the desired products 7-9 could be isolated in reasonably good yield by silica-gel and biobead column chromatography.…”

“…Generally speaking, the Q bands for a double-decker with a porphyrin moiety at the nonperipheral a position (that is, 7) are slightly red shifted compared with double-deckers with peripheral porphyrin unit(s) (that is, 8 and 9). [14] It is well known that single-hole-containing neutral bis(phthalocyaninato) rare earthA C H T U N G T R E N N U N G (III) complexes can be easily converted into the corresponding reduced form by using either hydrazine hydrate or NaBH 4 as the reducing agent. [17] Upon addition of hydrazine hydrate into a CHCl 3 / MeOH 3:1 solution of [Eu(Pc) 2 ], all of the three PcC À absorption bands at 461, 907, and 1599 nm disappeared.…”