Metallophthalocyanine dimers incorporating five-atom covalent bridges

Abstract

Metal-free copper and cobalt(II) binuclear phthalocyanines, in which the two phthalocyanine nuclci are covalently linked through five-atom bridges, have been prepared and characterized. Some new metal-free, copper, cobalt(II), and zinc 2,9,16,23-tetraalkoxyphthalocyanines, some of which are extremely soluble in organic solvents, are described.

Approaches towards the synthesis of a 2,9,16,23-tetrasubstituted phthalocyanine as a pure isomer

“…Virtually all tetrasubstituted phthalocyanines known in the literature (1) exist as a mixture of the four possible isomers, and in the case of substituents at the 2 position are usually referred to as the 2,9,16,23-tetrasubstituted isomer. On the other hand, in a very recent paper, Gaspard and Maillard (9) have succeeded in preparing the pure isomer 2,9,17,24-tetratert-butylphthalocyanine zinc(II), using metallic zinc as the condensing agent.In connection with our studies on multinuclear phthalocyanine (6,7,10) and with the possibility of obtaining one pure isomer of a binuclear phthalocyanine for X-ray diffraction studies, we were interested in exploring synthetic methods of '~uthor to whom correspondence may be addressed.phthalocyanine formation that could give rise exclusively to the 2,9,16,23-tetrasubstituted phthalocyanines as one isomer. In a previous paper we showed that dithioamides do form phthalocyanines with diiminoisoindolines at modest temperatures (1 1).…”

“…Most tetrasubstituted phthalocyanines are prepared by self-condensation of a suitable 3 or 4-substituted phthalonitrile or derivative (4,5). For example, the isoindoline of 4-neopentoxyphthalonitrile will, upon condensation, give not only 2,9,16,23-tetraneopentoxyphthalocyanine (1) but also the 2,10,16,24-, 2,9,17,24-, and 2,9,16,24-tetraneopentoxyphthalocyanine isomers (6,7). Indeed, we have shown that the 2,9,16,23-tetraneopentoxy hthalocyanine zinc(11) (2) derivative exhibited P peaks in its H nmr spectrum, indicating the presence of seven of the possible eight environments collectively present in the four isomers (7).…”

Multisubstituted phthalonitriles for phthalocyanine synthesis

“…The synthesis of sy.mmetrical tetra [3][4][5][6], oct^ 17-91, and even hexadecaphthalocyanine (Pcs) [10][11][12] are relatively straightforward using an appropriately substituted phthalonitrile as the sole precursor. In most examples these phthalonitrile precursors consist of phthalonitriles containing only one substituent at the 3-or 4-position or disubstituted phthalonitriles having two identical substituent$ on the 4,5-or 3,6-positions, but in one unusual example at the 3,4-position [3].…”

“…In most examples these phthalonitrile precursors consist of phthalonitriles containing only one substituent at the 3-or 4-position or disubstituted phthalonitriles having two identical substituent$ on the 4,5-or 3,6-positions, but in one unusual example at the 3,4-position [3]. For S-p-fert butylphenoxy -3,4,6-triff uorophthalo_ nitrile (6), Following the procedure described for g below, but using 3,4,5,6- 3,4,6-trifl uoro-5-p-methylphenoxyphthalonitrile (7). Following the procedure described for 8 below, but using 3j, 5,6-tetrafluorophthalonitrile (l), and p-methylphenol (4), a product was obtained which was chromatographed on flash grade silica gel using ethyl acetate I hexane (l:l) 3,4,6-trichloro-5-p.methylphenoxyphthalonitrile (9).…”

Synthesis and characterization of di-n-hexylamino-substituted phthalocyanines

“…The great solubility of some tetrasubstituted phthalocyanines results not only from the steric bulk of the substituents preventing aggregation, but also from the presence of the very similar isomers [18,19]. Thus, a mixture of similar isomers may practically be more useful than a single, less soluble isomer [20].…”