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An Easy Route for the Synthesis of New Axially Substituted Titanium( IV ) Phthalocyanines
Author(s) -
Barthel Markus,
Dini Danilo,
Vagin Sergej,
Hanack Michael
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200211)2002:22<3756::aid-ejoc3756>3.0.co;2-4
Subject(s) - chemistry , steric effects , titanium , phthalocyanine , axial symmetry , solubility , proton nmr , ligand (biochemistry) , photochemistry , combinatorial chemistry , stereochemistry , organic chemistry , structural engineering , engineering , biochemistry , receptor
A facile synthesis of highly soluble, axially substituted titanium( IV ) phthalocyanines is described. The reaction of tetra‐ tert ‐butylphthalocyaninatotitanium oxide t Bu 4 PcTiO with the chelating agents 3a − 3i containing oxygen or sulfur as donor atoms leads to the formation of axially substituted t Bu 4 PcTiX (X = functionalized catechols, dithiocatechol, and dihydroxynaphthalene). Following the same procedure a dimeric sandwich‐like complex could be also synthesized from the reaction of t Bu 4 PcTiO with tetrahydroxy‐ p ‐benzoquinone. All compounds were characterized by IR, UV/Vis, MS, 1 H and 13 C NMR spectroscopy, and elemental analysis. The axially substituted titanium phthalocyanines show high solubility and a low aggregation tendency due to the steric hindrance arising from the asymmetric peripheral substitution pattern of the macrocycle and the presence of bulky axial ligands. The relevant nonlinear optical (NLO) properties of some of the t Bu 4 PcTiX compounds were determined in order to evaluate the potential role of these new compounds in optical limiting. The correlation between t Bu 4 PcTiX structure and NLO properties is analyzed in terms of the electronic effects of the axial ligand.