Sandwich quadruple-decker binuclear lanthanide(III) complexes based on clamshell-type phthalocyanine ligand: synthesis and physicochemical studies. (November 2019)

• Record Type: Journal Article
• Authors: Korostei, Yuliya S.; Pushkarev, Victor E.; Tolbin, Alexander Yu.; Dzuban, Alexander V.; Chernyak, Alexander V.; Konev, Dmitry V.; Medvedeva, Tatyana O.; Talantsev, Artem D.; Sanina, Nataliya A.; Tomilova, Larisa G.
• Is Part Of: Dyes and pigments. Volume 170(2019)
• Publication Date: 2019-11
• Subjects: Phthalocyanines -- UV–Vis–NIR spectroscopy -- NMR spectroscopy -- Sandwich complexes; Dyes and dyeing -- Periodicals; Pigments -- Periodicals; 667.2
• DOI: 10.1016/j.dyepig.2019.107648
• Languages: English
• ISSNs: 0143-7208

Abstract

Abstract: A series of heteroleptic quadruple-decker bis[lanthanide(III)] complexes based on a flexible spacer-linked phthalocyanine ligand of clamshell-type, denoted sandwich-clamshell complexes, have been prepared. Complexation of 1, 1'-[benzene-1, 2-diylbis(methanediyloxy)]-bis[9(10), 16(17), 23(24)-tri- tert -butylphthalocyanine] ( clam, tBu Pc2 H4, 1 ) with [2(3), 9(10), 16(17), 23(24)-tetra- tert -butylphthalocyaninato] lanthanide(III) acetates [ tBu PcLnOAc, 2a – d ; Ln = Eu (a ), Gd (b ), Tb (c ), Lu(d )] afforded quadruple-deckers clam, tBu Pc4 Ln2 (3a – d ) with good to excellent yields. The complexes reveal intrinsic UV–Vis–NIR absorption by analogy to classical double-decker phthalocyaninates, while demonstrating high thermal stability up to 350 °C. At the same time, a combination of 1 H NMR, electrochemistry and SQUID magnetometry supported by DFT theoretical calculations indicates that bis(phthalocyanine) subunits in3 are in close contact mainly governed by the spacer group and, in some extent, by the presence of bulky tert -butyl peripheral substituents in the four phthalocyanine decks. Graphical abstract: Image 1 Highlights: The family of sandwich- clamshell phthalocyaninato quadruple-deckers was extended by Eu, Gd and Tb compounds. Conditions for the rational synthesis were found with a multiple increase in the yield compared to literature. A complex physicochemical and theoretical study of sandwich- clamshell quadruple-deckers was first conducted. Electrochemistry reveals specific intramolecular π-system interactions NMR and SQUID data show the existence of intramolecular magnetic interactions.