Institute of Problems of Chemical Physics RAS, Department of Kinetics and catalysis, 142432, Russian Federation.
Institute of Solid State Physics RAS, 142432, Russian Federation.
Chemistry. 2018 Jun 12;24(33):8415-8423. doi: 10.1002/chem.201800873. Epub 2018 May 15.
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) Ti (Pc )}(Cl )⋅C H Cl (1), {cryptand(K )}{(cis-thioindigo-O,O) In (Pc )} ⋅C H Cl (2), and {cryptand(K )}{[(SQ) -O,O] In (Pc )} ⋅3.5 C H Cl (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 Pc or In Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ ) dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In Pc. Dianionic Pc 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.
已经开发出用于制备钛(IV)和铟(III)酞菁（Pc）与有机染料（如靛蓝、硫靛和方酸染料 III（SQ））的配位配合物的还原方法，这些方法可以得到结晶的{cryptand(K )}{(cis-indigo-O,O) Ti (Pc )}(Cl )⋅C H Cl（1）、{cryptand(K )}{(cis-thioindigo-O,O) In (Pc )} ⋅C H Cl（2）和{cryptand(K )}{[(SQ) -O,O] In (Pc )} ⋅3.5 ⋅C H Cl（3）配合物。这些配合物的形成伴随着起始染料还原为阴离子态。在 1 和 2 中，反式靛蓝或反式硫靛向顺式构象的转变提供了染料的两个羰基氧原子与 Ti Pc 或 In Pc 的配位。SQ 被还原为自由基阴离子态，并在 3 中形成不寻常的抗磁性单键（SQ）二聚体。这些二聚体具有两个紧密定位的羰基氧原子与 In Pc 配位。在 1-3 中发现了二阴离子 Pc 大环。这些配合物在一个金属中心含有两个发色团分子。然而，它们的光学光谱主要由金属酞菁的吸收带定义。
