The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8 a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhyrazine 8, respectively, by oxidation with Pb(OAc)₄ in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8 a was studied in detail. These species not only easily undergo Diels–Alder additions with dienes, but also the used solvents can be added. Among the addition products with solvents ethoxy-, acetoxy-, acetoxybutyloxy-substituted and barrelen-fused phthalocyanines and benzoporpyrazines were isolated. No products resulting from the dimerization of two dehydro species were observed either for 2 or 8 a. Analysis of the reaction products in comparison with those obtained by oxidation of 1-aminobenzotriazole 15 under similar conditions proves a higher reactivity (electrophilicity) of the dehydro-PcZn 2 and dehydro-PzZn 8 a in comparison with unsubstituted benzyne towards the solvents used, such as diethyl ether and benzene.

Photostable naphthalocyanines (see Figure) can act as optical limiters, simultaneously absorbing nanosecond laser pulses at 532 nm and 1064 nm. In these naphthalocyanines, where M can correspond to Zn, InCl, or In(p-trifluoromethylphenyl), the pattern of substitution and the nature of the substituents were found to be critical factors in achieving such a combination of linear and nonlinear optical properties.

Direct 1N-amination of the triazole-fused zinc phthalocyanine 2 and oxidation of the formed amino derivative 3 resulted in the generation of the very reactive intermediate, the dehydrometallophthalocyanine 4, which was not known previously. The latter was trapped in situ with different dienes, for example, furan, tetraphenylcyclopentadienone, and anthracene to form the corresponding Diels–Alder adducts. The products were characterized by ¹H and ¹³C-dept135 NMR, and UV/Vis spectroscopy, MALDI-TOF mass spectrometry, and elemental analysis, which are fully in agreement with their structure. The developed synthetic procedure opens a simple and versatile pathway towards unsymmetrical peripheral modification of phthalocyanines, which is readily applicable to the micromol scale and is important for the design of new interesting Pc-based systems.

The monomeric octaethylhexyl- and tetra-tert-butyl-substituted phthalocyanines 3 and 12 with axial acetylacetonate as ligands were synthesized and characterized, in order to compare their optical limiting properties with the state-of-the-art molecule [tetra-(tert-butyl)phthalocyaninato]indium chloride (tBu)₄PcInCl (1a) and the phthalocyanines 1b−f. In addition, the trimer 17 was also synthesized (as a mixture of isomers). The synthesis of 3, 12 and 17 was carried out by refluxing the corresponding metal-free phthalocyanines, (tBu)₄PcH₂ (2), (RO)₈PcH₂ (6) (R = 2-ethylhexyl) and the trimer 16 with an excess of In(acac)₃ in DMF. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

A series of new axially bis-coordinated (octaphenylporphyrazinato)ruthenium(II) complexes {[(Ph₈Pz)RuL₂], L = cyclohexyl isocyanide, CyNC, (1b); 4,4′-bipyridine, bpy, (2c); N-methylimidazole, CH₃Im, (3a)} was prepared and characterized. The reaction of the bis-isocyanide adducts [(Ph₈Pz)Ru(tBuNC)₂] (1a) or [(Ph₈Pz)Ru(CyNC)₂] (1b) with monodentate N-heterocycles gave, under certain conditions, the mixed-ligand complexes [(Ph₈Pz)Ru(Py)(tBuNC)] (4a), [(Ph₈Pz)Ru(Py)(CyNC)] (4b) and [(Ph₈Pz)Ru(CH₃Im)(CyNC)] (3b). The reaction of 1a or 1b with an excess of bidentate 4,4′-bipyridine under the same conditions resulted in the formation of the corresponding dimeric species [(Ph₈Pz)Ru(tBuNC)]₂(μ-bpy) (2a) and [(Ph₈Pz)Ru(CyNC)]₂(μ-bpy) (2b) in high yield. The structures of all the complexes were unambiguously proved by ¹H NMR spectroscopy, and the possibility of their self-assembly is discussed. All mixed-ligand compounds were also characterized by UV/Vis and IR spectroscopy, as well as elemental analysis. The ¹H NMR spectra of these compounds are discussed in detail. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The preparation of new octakis[m-(trifluoromethyl)phenyl]- and octakis[m-(trifluoromethyl)phenoxy]phthalocyanines (6a and 6b) and their complexes with magnesium (5a, 5b) and indium (7a, 7b) is described. Their spectroscopic properties and solubilities are discussed in relation to those of metal-free and metallated octakis[m-(trifluoromethyl)phenyl]porphyrazine, as well as those of metal m-(trifluoromethyl)phenyl- and m-(trifluoromethyl)phenoxy-substituted 2,3-naphthalocyanines. A drastic decrease in the solubilities of the metal-free phthalocyanines in CH₂Cl₂ was observed on comparing them with m-CF₃-phenyl-substituted porphyrazine. However, their solubilities in THF were high enough for NMR spectra to be recorded. Insertion of (chloro)indium into the cavities of these phthalocyanines noticeably enhances the solubilization of the macrocycles, including in CH₂Cl₂. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The reactivity of the 2,3-dibromobenzo-annulated 2,3,7,8,12,13-hexakis(m-trifluoromethylphenyl)porphyrazine magnesium complex 1 towards butyllithium and tert-butylmagnesium chloride in the presence of metallic magnesium was studied. It was found that n-butyllithium reacts mainly with the porphyrazine macrocycle to give tetraazachlorins and other reduction products, similarly to porphyrins. On treatment of 1 with tBuMgCl and Mg, dehydroporphyrazine 4 (arynoporphyrazine) was generated and trapped with furan, confirming the possibility of the formation of a dehydrophthalocyanine. The structures of the products were verified by UV/Vis and NMR spectroscopy, and also mass spectrometry (MALDI-TOF). Utilization of the tetrapyrrolic macrocycle 1 for this type of reaction may become a new synthetic strategy for unsymmetrical peripheral derivatization of phthalocyanines and related compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

An easy route for the synthesis of vanadium, zinc, magnesium, etc. complexes of new soluble symmetrical octa(m-trifluoromethylphenyl) or octa(m-trifluoromethylphenoxy) substituted 2,3-naphthalocyanines {[(m-CF₃Ph)₈NcM] or [(m-CF₃PhO)₈NcM]} in good yields is described in detail. The structures of the synthesized compounds were verified by UV/Vis and ¹H and ¹³C NMR spectroscopy, as well as by mass spectrometry. The good solubilities of the prepared compounds in toluene and coordinating solvents (e.g., THF), was explained in terms of the nonplanar arrangements of eight m-CF₃Ph substituents in relation to the Nc macrocycle, preventing aggregation of the molecules. The Q-bands in the UV/Vis spectra of the [(m-CF₃Ph)₈NcM] species are each bathochromically shifted by ca. 13 nm in relation to [(m-CF₃PhO)₈NcM] species, appearing at 817 nm for [(m-CF₃Ph)₈NcVO] in toluene. All NcMs prepared exhibit very high molar extinction coefficients for the Q-band {lg(ϵ) ≈ 5.6} in THF. Some of prepared Nc complexes appeared to be very unstable on exposure to daylight. In addition, a nickel-catalyzed Kumada cross-coupling synthesis of substituted o-terphenyls, intermediate compounds for the preparation of octaaryl-substituted Ncs, is described. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The unsymmetrical binuclear phthalocyanine 4a and the symmetrical binuclear phthalocyanine 4b with two different metals (Ni and Cu), as well as the correspondent binuclear phthalocyanines with two Ni atoms (4c and 4d) were synthesized from the benzoannulated dicyano-substituted Ni phthalocyanine 2. Atomic absorption spectroscopy verified unambiguously the presence of Ni and Cu in the binuclear phthalocyanines. The proposed synthetic route demonstrates great versatility towards substitution at the peripheral positions of the ring and the variation of the chelating central metal. Complexes 4a−4d are soluble in common organic solvents of medium polarity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The fluorine-containing metal naphthalocyanines [F₁₆NcGaCl] (7) and [(F₁₆NcGa)₂O] (8), which represent the first examples of peripherally fluorine substituted naphthalocyanines, were synthesized, and the nonlinear optical transmission was studied. Peripheral substitution by fluorine atoms enhances the solubility and photostability of the naphthalocyanines. In particular, for the axially μ-oxo-bridged naphthalocyanine dimer 8, practically no aggregation was observed in organic solvents and it has proved to be an efficient optical limiter when irradiated with laser light pulses at the wavelength of 532 nm, with pulse duration of 5 ns and repetition rate of 20 Hz.

A facile synthesis of highly soluble, axially substituted titanium(IV) phthalocyanines is described. The reaction of tetra-tert-butylphthalocyaninatotitanium oxide tBu₄PcTiO with the chelating agents 3a−3i containing oxygen or sulfur as donor atoms leads to the formation of axially substituted tBu₄PcTiX (X = functionalized catechols, dithiocatechol, and dihydroxynaphthalene). Following the same procedure a dimeric sandwich-like complex could be also synthesized from the reaction of tBu₄PcTiO with tetrahydroxy-p-benzoquinone. All compounds were characterized by IR, UV/Vis, MS, ¹H and ¹³C 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 tBu₄PcTiX compounds were determined in order to evaluate the potential role of these new compounds in optical limiting. The correlation between tBu₄PcTiX structure and NLO properties is analyzed in terms of the electronic effects of the axial ligand.

The synthesis and characterization of the highly soluble tetra(tert-butyl)gallium(III) phthalocyanines (tBu)₄PcGaCl (2) and (tBu)₄PcGa(p-TMP) (3) is described. They were characterized by IR, UV/Vis, MS, and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Verstärkte nichtlineare optische Eigenschaften werden bei einem löslichen dimeren Indium-Phthalocyanin(Pc)-Komplex beobachtet, der als Lewis-Base-Addukt stabilisiert wird. Die In-Zentren liegen etwas außerhalb der makrocyclischen Ringebenen, und die Pc-Liganden sind bezüglich der In-In-Achse um 14.5° gekippt (siehe Bild). Der In-In-Abstand wurde durch EXAFS-spektroskopische Messungen zu 3.24 Å bestimmt.

An overview of the optical limiting (OL) processes in phthalocyanines and related compounds is presented, particularly a description of the synthesis and relevant optical properties of a series of axially substituted indium(III), titanium(IV), phthalo- and naphthalocyanines, and octaarylporphyrazines. Several techniques, such as transient absorption, Z-scan, and degenerate four-wave mixing, were used to assess the optical properties and OL performance of the investigated compounds. The versatility of the methods of organic synthesis leads to the achievement of effective systems in terms of OL performance through the appropriate combination and modulation of several structural components. The chemistry of the macrocycles here considered allows the variation of the different chemical features, such as the degree of electronic conjugation of the macrocycle and the nature of the ring substituents, the central atom, and the ligands attached to the central atom. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 129–148, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10024

Highly soluble [(tBu₄PcM)₂O] phthalocyanine dimers (M=Ga^III (3), In^III (4)) were prepared by the reaction of [tBu₄PcMCl] (M=Ga^III (1), In^III (2)) with excess of concentrated H₂SO₄ at −20 °C. The MOM linkages in 3 and 4 are not stable against concentrated H₂SO₄ at room temperature, 6 n HCl at reflux, or during isolation under column chromatographic conditions (e.g. silica gel/toluene). The stability of 3 in solution is considerably higher than that of 4. The μ-oxo-bridged phthalocyanine dimers 3 and 4 have a more intense photoluminescence emission in the red region than the monomers 1 and 2. The gallium phthalocyanines 1 and 3 have fluorescence lifetimes of a few nanoseconds, while those of the indium phthalocyanines 2 and 4 last for only several hundred picoseconds. Comparison of the fluorescence lifetimes of monomers 1 and 3 with dimers 2 and 4, reveals that the dimers have longer lifetimes of the excited singlet states. The transient absorption spectrum is similar for all of the compounds, and the transient absorption band at about 520 nm, observed by nanosecond laser irradiation, can be assigned to the transition from the lowest triplet excited state to the upper triplet excited states (T–T absorption). The magnitude of the optical limiting exhibited by 1, 3, and 4 in toluene at 532 nm laser pulse irradiation is in the order: 3>4>1. The values of the imaginary third-order nonlinear susceptibility Im{χ⁽³⁾} of the above compounds at 532 nm in toluene are also reported. These results demonstrate that these compounds are candidates for optical limiting applications.

The synthesis of a complete series of nine soluble distyrylbenzenes (DSBs) with two (2a−c) and four cyano groups (1a−f) attached to the peripheral aromatic rings is reported. They were prepared by the Wittig reaction and characterized by ¹H and ¹³C NMR, FT-IR, UV/Vis, PL, EL, mass spectra, and elemental analysis. The optical properties have been studied in detail to monitor structure−luminescence relationships as a function of the position of the cyano moieties. The DSBs with cyano substituents show bathochromic shifts in their absorption spectra when compared to the parent DSB (30). The extent of this red-shift depends on electronic and steric factors. The bis(p-cyano)-substituted compound 2c exhibits a small Stokes shift and a remarkably high quantum yield of ϕ_F = 0.6−0.8 in the solid state. All the new distyrylbenzenes show electroluminescence when employed in devices with an ITO/PcCu/DSB/Al configuration and with colors ranging from red to green.

This work gives an overview concerning the optical limiting processes in phthalocyanines. In particular, the synthesis and the relevant optical properties of a series of axially substituted indium(III)− and titanium(IV)−phthalo- and -naphthalocyanines are described. Several techniques, such as transient absorption, Z-scan, and degenerate four-wave mixing, have been used for assessing the optical properties and optical limiting performance of the investigated compounds.

To obtain more information about the structure of phthalocyaninatoruthenium compounds an EXAFS investigation was carried out on amorphous bisaxially bridged phthalocyaninatoruthenium(II) oligomers, [PcRu(tz)]_n (1), [PcRu(pyz)]_n (2) and [PcRu(dib)]_n (3). Detailed structural models for the three compounds were deduced from the determined atomic distances around the metal center. A bisaxial structure of the ligands could be proven for all compounds and additionally, the structure parameters could be determined.

The syntheses of highly soluble chloro(naphthalocyaninato)indium(III) compounds (R²)₄(R⁴)₄NcInCl (5a: R² = H, R⁴ = tert-butyl; 6a: R² = R⁴ = tert-butyl; 7a: R² = 2-ethylhexyloxy, R⁴ = tert-butyl; 8a: R² = R⁴ = 2-ethylhexyloxy), and their reactions with R′MgBr [b: R′ = p-(trifluoromethyl)phenyl; c: R′ = pentafluorophenyl] producing the axially substituted aryl(naphthalocyaninato)indium(III) compounds 5b, 5c, 6b, 6c, 7b, 7c, 8b, and 8c are described. All compounds were characterized by IR, UV/Vis, MS, and ¹H, ¹³C, and ¹⁹F NMR, as well as by elemental analysis. The high solubilities of the octasubstituted naphthalocyanines 6−8 and their low tendencies to form aggregates are due to steric crowding arising from the new unsymmetrical peripheral substitution pattern and the bulky, electron-withdrawing axial ligands. These properties make the (naphthalocyaninato)indium compounds very interesting candidates for further investigations concerning their nonlinear optical properties, particularly for optical limiting applications. We also report on the complete syntheses and characterization of the corresponding diiminoisoindoline precursors 2 (R² = R⁴ = tert-butyl), 3 (R² = 2-ethylhexyloxy; R⁴ = tert-butyl) and 4 (R² = R⁴ = 2-ethylhexyloxy).

The poly-para-phenylenevinylene (PPV) model compound 1 with cyano groups on the vinylene moieties and 2-ethylhexyloxy chains on the central phenylene unit has been synthesized by Knoevenagel condensation of 1,4-bis(cyanomethyl)-2,5-bis(2-ethylhexyloxy)benzene and benzaldehyde. The only isomer that was obtained has been identified to have the Z,Z configuration. UV irradiation of the Z,Z isomer 1a in solution with a medium-pressure mercury lamp gave a mixture of all three possible isomers (Z,Z, Z,E and E,E; 1a, 1b and 1c respectively). The isomers were separated by column chromatography and identified spectroscopically. Electrochemical studies and fluorescence emission spectra of 1a and 1c are reported. The substituted PPVs 2, 3 and 4 have been synthesized and their absorption and emission spectra before and after UV irradiation are compared. Copyright © 2001 John Wiley & Sons, Ltd.

The 2(3),9(10),16(17),23(24)-tetrasubstituted metalphthalocyanines 1–7 (M=In, Ni, Zn) were synthesized, as mixtures of four different structural isomers, from the corresponding 4-alkoxy-1,2-dicyanobenzenes and the appropriate metal salts. Separation of the four structural isomers was successfully achieved on a C₃₀ alkyl phase by high-performance liquid chromatography (HPLC). The determination of the point groups of the structural isomers was carried out for 1 and 3, the composition of the structural isomers of 4–7 was accomplished by comparing their retention times and UV/Vis spectra with the data of 1 and 3. For the phthalocyanines 8–10 and the naphthalocyanines 11 and 12 only the C_4h and D_2h isomers could be separated.

Die Synthese von neuen 2,3-tetraalkenyloxy substituierten Phthalocyaninen mit verschieden langen Alkenylketten und unterschiedlichen Zentralmetallen, sowie die Separierung der vier Strukturisomere mittels HPLC (C₃₀-Phase) ist Thema dieser Arbeit. Charakterisierung der einzelnen Isomere erfolgte durch ¹H NMR- und UV/Vis-Spektroskopie. Die Untersuchung des sterischen Einflusses der Substituenten sowie der Einfluß des Zentralmetalls auf den Trennprozess und die Isomerenzusammensetzung ist hierbei von besonderem Interesse.

The condensation of substituted diiminoisoindolines with alkyl-substituted 1,3,3-trichloroisoindolines results in the formation of the highly soluble metal-free phthalocyanines 9, 15. By the same methodology, metal-containing phthalocyanines such as 16, 18 are accessible from suitable metal salts. The precursors 24 and26 were obtained from the phthalocyanine 9 and tetracyclone. The generation of the phthalocyanines 23 and 25 possessing isobenzofuran moieties as diene subunits was accomplished; in the presence of excess 28, the tetracyclone-bisadducts 22 and 24 were transformed into the model compounds 29 and 30, while an excess of 20 or 9 leads to the appropriate trimer-oligomers 31 and 32.

To obtain more structural information of (phthalocyaninato)ruthenium compounds, an EXAFS investigation was carried out on amorphous tBu₄PcRu (1), tBu₄PcRu(3-Clpy)₂ (2), PcRu(3-Fpy)₂ (3) and (C₅H₁₁O)₈PcRu(3-Clpy)₂ (4). Structural models for the four compounds are deduced from the atomic distances determined around the metal centre. A dimeric structure was found for 1, while bisaxial arrangement of the ligands was shown for 2, 3 and 4, and the structural parameters were also determined.

The synthesis of new nitrido(phthalocyaninato)molybdenum (1–4) and -tungsten complexes (5–7) starting from the corresponding phthalonitriles and MNCl₃ (M = Mo, W) is reported. In addition, the reaction of (tBu₄Pc)WN (6) with PPh₃ leading, after several steps, to the diamagnetic compound (tBu₄Pc)WO (7) is described. The reaction of (tBu₄Pc)ReN (9) with PPh₃ leads to [(tBu₄Pc)ReO]₂ (12), and of [(C₅H₁₁)₈Pc]ReN (10) with PPh₃ leads, under different conditions, to {[(C₅H₁₁)₈Pc]ReO}₂O (11).

An easy synthesis of phthalocyaninatotitanium(IV) compounds substituted with bidentate ligands in the axial position is described. Using strongly chelating oxygen or sulfur donor ligands, the reaction of PcTiO with chelating agents leads to the formation of PcTiX complexes with X ≡ oxalate () (2a), catecholate () (2b), dithiocatecholate () (2j), 2,3-dihydroxynaphthalene () (2i) and other functionalized catechols (2c–2h). The new compounds possess an enhanced solubility in comparison to PcTiO. Copyright © 2000 John Wiley & Sons, Ltd.

Symmetric, peripherally substituted dihydroxysilicon tetrapyrazinoporphyrazines 5 and 6 were synthesized by reacting the diiminoisoindolines 1 and 2 with SiCl₄ in pyridine as solvent at considerably low temperature followed by hydrolysis of the intermediate dichlorosilicon tetrapyrazinoporphyrazines 3 and 4. In addition, the preparation of the bisaxially substituted trialkylsilyloxysilicon tetrapyrazinoporphyrazines 11 and 12, the corresponding trialkylsilyloxyhydroxy compound 14 and the µ-oxo dimer 15 is also reported. Copyright © 2000 John Wiley & Sons, Ltd.

A series of oligomers analogous to poly(p-phenylenevinylene) (PPV), combining naphthalene and benzene as aromatic units, have been synthesized by a Knoevenagel reaction. By measuring UV/Vis spectra, photoluminescence (PL) and electroluminescence (EL), we studied the influence of the position of the naphthalene unit as well as the steric and electronic influences of cyano and alkyloxy substituents on the luminescent properties of these compounds.

Die systematische Synthese und Charakterisierung von acht neuen PPV-analogen Modell-Verbindungen mit photo- und elektrolumineszenten Eigenschaften ist Thema dieser Arbeit. Besonderes Interesse liegt auf der Untersuchung der sterischen und elektronischen Einflüsse von Cyano-Gruppen und Hexyloxy-Ketten an den Phenyl- und Naphthyl-Einheiten des konjugierten Systems. Durch Variation dieser Reste können die optischen Eigenschaften dieser Verbindungen stark modifiziert werden.

The reactions of nitrido(tetra-tert-butylphthalocyaninato)rhenium (1) with boron tribromide leading to (tBu₄Pc)ReNBBr₃ (4) and with acetone to give the imido complex (tBu₄Pc)Re[NC(CH₃)₂CH₂C(O)CH₃]OH (2b) and its μ-oxo dimer 3 are reported. Starting from the corresponding 4,5-di-n-alkylphthalonitriles and ammonium perrhenate four soluble nitrido(octa-n-alkylphthalocyaninato)rhenium complexes 5–8 were synthesized. Nitrido(octa-n-pentylphthalocyaninato)rhenium (6) was treated with boron tribromide to afford [(C₅H₁₁)₈Pc]ReNBBr₃ (9).

The synthesis of several new phthalonitriles 3, 9, 14, 25, 33, and 36, functionalised with carboxyl groups, including two examples of amino acid derivatives is described. All new phthalonitriles were converted into their corresponding phthalocyaninatozinc compounds. The phthalocyanines, 2,3,9,10,16,17,23,24-octa(1-carboxyethyloxy)phthalocyaninatozinc (5), 2,9,16,23-tetra(2-amino-2-carboxyethyl)phthalocyaninatozinc (11), 2,9,16,23-tetra(1-carboxy-2-hydroxyethylaminocarbonyl)phthalocyaninatozinc (16), 1,8,15,22-tetra(carboxybutyl)phthalocyaninatozinc (27), 2,3,9,10,16,17,23,24-octa(carboxyalkyl)phthalocyaninatozinc (39), and the nonidentically substituted 9,10,16,17,23,24-hexa(carboxyalkyl)-2-[4-(N-succinimidyloxycarbonyl)butyl]phthaloyaninatozinc (41) are all sufficiently soluble in water. The nonidentically-substituted compounds are important due to their selective binding to tumor-selective antibodies. UV/Vis-spectroscopy was used to investigate the effect of more or less sterically-demanding substituents in the periphery of the phthalocyanines towards aggregation. The phototoxicity towards cancer cells of some of the new compounds was investigated in several in-vitro experiments.

The octasubstituted (phthalocyanine)nickel complexes 4a,b, soluble in common organic solvents, bearing four dienophilic functionalities were synthesized from the corresponding phthalodinitriles 3a,b and nickel(II) acetate. Reaction of 4a with tetracyclone 5 led to the phthalocyanine–tetracyclone adduct 6 which is a precursor for an intermediate phthalocyanine 7 containing four isobenzofuran moieties. The capability of 7 to react as tetrakis(diene) was demonstrated by its reaction with naphthoquinone. Furthermore, the unsymmetrical phthalocyanines 13 and 16a,b,c containing one dienophilic functionality were synthesized using a statistical approach. Their tetracyclone adducts 17, 18a,b,c can be used for the synthesis of ladder-type phthalocyanine dimers. The dimer 22 was synthesized from 18c and p-benzoquinone via the isobenzofuran intermediate 19 and the benzoquinone adduct 21. For dehydration experiments the naphthoquinone monoadduct 23 was synthesized from 18c. Dehydration of 22 and 23 was carried out successfully with p-toluenesulfonic acid. The Diels–Alder reactions are discussed with respect to the occurring exo/endo ratio.

The nickel phthalocyanine 4, which is soluble in common organic solvents, has been synthesized from the corresponding tetracyclone monoadduct 1 and acrolein (3). Reaction of 4 with p-toluenesulfonic acid leads to the modified phthalocyanine monoaldehyde 5. The capability of 5 to undergo a Wittig reaction has been demonstrated with benzyltriphenylphosphonium bromide (6). Furthermore, a dimer 9 has been synthesized by treating 5 with 0.5 equiv. of xylylenebis(triphenylphosphonium bromide) (8). Dimer 9 constitutes a model compound for corresponding PPV polymers containing phthalocyanine subunits.

Several 1(4)- and 2(3)-tetraalkoxy-substituted phthalocyanines (shown) were synthesized from the corresponding (R,S)-, (R)-, and (S)- alkoxy-substituted phthalonitriles, and the four structural isomers formed for each phthalocyanines were separated by HPLC. The influence of (R,S)-, (R)-, and (S)-substituents on the isomer distribution of the formed phthalocyanines is discussed. M = Cu, Ni, Zn.

The previously reported reaction of phthalocyanines [H₂(pc)] with PBr₃, which was claimed to give a phosphorus(III) phthalocyanine “(PcP^III)”, has been reinvestigated in detail with both unsubstituted and alkyl-substituted phthalocyanines, 1-4. The products exhibit unusual electronic and mass spectra compared to normal phthalocyanines and have been identified as oxophosphorus(V) triazatetrabenzcorroles 5–8. The corresponding dihydroxyphosphorus(V) phthalocyanine hydroxides 9–12 have also been synthesized for the first time by insertion of phosphorus(V) into phthalocyanines and have been characterized in detail. The different reactivities of PBr₃ and POX₃ (X = Cl, Br) toward phthalocyanines are discussed.

The synthesis of highly soluble chloro(phthalocyaninato)indium(III) complexes R_xPcInCl (3a: R¹ = tert-butyl, R² = H, x = 4 and 4a: R¹ = R² = n-pentyl, x = 8), and their reactions with R′MgBr [R′ = p-trifluoromethylphenyl- (b), m-trifluoromethylphenyl- (c), p-fluorophenyl- (d), perfluorophenyl- (e)] leading to the stable σ-bonded aryl(phthalocyaninato)indium(III) complexes 3b−e, 4b−e are described. All compounds were characterized by IR, UV/Vis, MS, ¹H, ¹³C and ¹⁹F NMR as well as elemental analyses. Phenyl(phthalocyaninato)indium(III) (4f) was prepared by the reaction of (n-C₅H₁₁)₈PcInCl (4a) with PhLi. The high solubility of the complexes 3a−e and 4a−f is, aside from the influence of the peripheral substituents, considered to be derived from the large dipole moments present which are due to the strongly electron withdrawing axial ligands, and from the lower tendency of axially substituted phthalocyaninato metal complexes to form aggregates.

The specific synthesis of a metal-free bisdienophilic phthalocyanine 193, suitable for repetitive Diels-Alder reactions, is reported. This was achieved by condensation of 191,3,3-trichloro-6/7-nitroioindolenine (191) and 4,9-dibutoxy-2,3,5,8-tetrahydro-1,3-diimino-1H-5,8-epoxybenz[f]isoindoline (2). The ability of 3 to undergo Diels-Alder reactions was tested by reaction with an excess of 1,2,3,4-tetraphenylcyclopentadienone (5). Experimental data of the hemiporphyrazines 9, 10, and 11, which can be used as precursors for the synthesis of ladder polymers, are also given in the Experimental Section.

Octa-tert-butylphthalocyanina-tonickel(II) (4) was synthesized from 3,5-di-tert-butylphthalonitrile (1) and nickel acetate. A nonstatistical mixture of the four structural isomers 4a–d was obtained. The isolation of the structural isomers 4a–d by preparative HPLC (MPLC) allowed their unequivocal identification and characterization by spectroscopic techniques. Moreover, a new family of tert-butyl-substituted phthalocya-nines 6–10 containing dienophilic functionalities were prepared by condensation of 3,5-di-tert-butylphthalonitrile (1) with 6,7–dicyano-1,4-epoxy-1,4-dihydronaphthalene (5). The separation of the phthalocyanines 6–10 and of some of their structural isomers was accomplished by normal column chromatography. The structural isomers were characterized by spectroscopic methods in terms of their symmetry.