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Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl‐Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers
Author(s) -
Konarev Dmitri V.,
Kuzmin Alexey V.,
Khasanov Salavat S.,
Fatalov Alexey M.,
Yudanova Evgenia I.,
Lyubovskaya Rimma N.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800873
Subject(s) - chemistry , chromophore , cryptand , metal , molecule , oxidation state , photochemistry , phthalocyanine , crystallography , ligand (biochemistry) , inorganic chemistry , stereochemistry , medicinal chemistry , ion , organic chemistry , biochemistry , receptor
Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K + )}{( cis ‐indigo‐ O , O ) 2− Ti IV (Pc 2− )}(Cl − ) ⋅ C 6 H 4 Cl 2 ( 1 ), {cryptand(K + )}{( cis ‐thioindigo‐ O , O ) 2− In III (Pc 2− )} − ⋅ C 6 H 4 Cl 2 ( 2 ), and {cryptand(K + )}{[(SQ) 2 ‐ O , O ] 2− In III (Pc 2− )} − ⋅ 3.5 C 6 H 4 Cl 2 ( 3 ) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans ‐indigo or trans ‐thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti IV Pc or In III Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ − ) 2 dimers in 3 . These dimers have two closely positioned carbonyl oxygen atoms coordinated to In III Pc. Dianionic Pc 2− macrocycles have been found in 1 – 3 . The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines.