Sandwich double-decker lanthanide(III) "intracavity" complexes based on clamshell-type phthalocyanine ligands: synthesis, spectral, electrochemical, and spectroelectrochemical investigations.
Phthalocyanine compounds of novel type based on a bridged bis-ligand, denoted "intracavity" complexes, have been prepared. Complexation of clamshell ligand 1,1'-[benzene-1,2-diylbis(methanediyloxy)]bis[9(10),16(17),23(24)-tri-tert-butylphthalocyanine] ((clam,tBu)Pc(2)H(4), 1) with lanthanide(III) salts [Ln(acac)(3)]⋅n H(2)O (Ln = Eu, Dy, Lu; acetylacetonate) led to formation of double-deckers (clam,tBu)Pc(2)Ln (2 a-c). Formation of high molecular weight oligophthalocyanine complexes was demonstrated as well. The presence of an intramolecular covalent bridge affecting the relative arrangement of macrocycles was shown to result in specific physicochemical properties. A combination of UV/Vis/NIR and NMR spectroscopy, MALDI-TOF mass-spectrometry, cyclic voltammetry, and spectroelectrochemistry provided unambiguous characterization of the freshly prepared bis-phthalocyanines, and also revealed intrinsic peculiarities in the structure-property relationship, which were supported by theoretical calculations. Unexpected NMR activity of the paramagnetic dysprosium complex 2 b in the neutral π-radical form was observed and examined as well.
Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russian Federation. pushkarev@org.chem.msu.ru
Victor E
VE
Pushkarev
Alexander Yu
AY
Tolbin
Fedor E
FE
Zhurkin
Nataliya E
NE
Borisova
Stanislav A
SA
Trashin
Larisa G
LG
Tomilova
Nikolay S
NS
Zefirov
D004563:Electrochemistry; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry*; D054833:Isoindoles; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure
D007211:Indoles; D054833:Isoindoles; D028581:Lanthanoid Series Elements; D008024:Ligands; C013647:phthalocyanine