Heteroleptic Rare Earth Double-Decker Complexes with Naphthalocyaninato and Phthalocyaninato Ligands. General Synthesis, Spectroscopic, and Electrochemical Characteristics

Abstract

A novel one-pot procedure starting from the corresponding M(acac)3 x nH2O, metal-free phthalocyanine H2Pc', and naphthalonitrile in the presence of DBU in n-octanol has been developed to prepare heteroleptic (naphthalocyaninato)(phthalocyaninato) rare earth double-decker complexes. A series of six sandwich compounds with different naphthalocyaninato ligands, phthalocyaninato ligands, and central rare earth metals, namely, Sm[Nc(tBu)4](Pc) [Nc(tBu)4 = 3(4),12(13),21(22),30(31)-tetra(tert-butyl)naphthalocyaninato; Pc = unsubstituted phthalocyaninato] (1), Sm(Nc)(Pc') [Pc' = Pc(OC5H11)4, Pc(OC8H17)8; Nc = 2,3-naphthalocyaninato; Pc(OC5H11)4 = 2(3),9(10),16(17),24(25)-tetrakis(3-pentyloxy)phthalocyaninato; Pc(OC8H17)8 = 2,3,9,10,16,17,24,25-octakis(octyloxy)phthalocyaninato] (2, 3), and M(Nc)[Pc(alpha-OC5H11)4] [M = Sm, Eu, Y; Pc(alpha-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] (4-6), have been isolated in good yields from this one-pot procedure demonstrating the generality of this synthetic pathway. In addition to spectroscopic analyses, the electrochemistry of these novel compounds has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods.

A series of homoleptic bis(phthalocyaninato) rare earth sandwich complexes with large two-photon absorption cross-section

“…The sandwich nature of these complexes has been confirmed by a wide range of spectroscopic methods including mass spectrometry, 1 H NMR, electronic absorption, and infra-red (IR) spectroscopy in addition to the elemental analysis [30][31][32][33][34]. Electronic absorption spectra were recorded with a Shimadzu UV-3600 spectrophotometer.…”

Single‐Ion Magnet Investigation of ABAB‐Type Tetrachloro‐ and Tetraalkoxy‐Substituted Bis(phthalocyaninato) Terbium Double‐Decker with D2 Symmetrical Ligand Field

“…Figure S3 (Supporting Information) displays the IR spectra of 1 and 2 . As can be seen, the absorption bands contributed from the phthalocyanine ring are observed, including the wagging and torsion vibrations of the C–H groups and isoindole ring stretching vibrations (745 cm –1 and 1154 cm –1 ) as well as the C=N aza group stretching vibrations (2250 cm –1 ) of phthalocyanine chromophore . The middle absorption bands at 2859–2926 cm –1 are due to the C–H stretching vibrations of the –CH 2 – and –CH 3 groups of –OC 5 H 11 groups in the IR spectrum of the compound.…”

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

“…Double deckers {Ln(Nc)[Pc(a-OPent) 4 ]} (Ln = Sm, Eu, Y) feature four oxidation and five reduction processes; DE o1-r1 is almost constant, 0.34-0.35 V, while DE r1-r2 , which represents the HOMO-LUMO gap of the reduced forms {Ln(Nc)[Pc(a-OPent) 4 ]} À , decreases from 1.21 V to 1.16 V and 1.09 V for Sm, Eu, and Y, respectively. 253…”