The first synthesis of pure tert-butyl-substituted (phthalocy-3-chloropyridine, ammonia) is described. The compounds aninato)-and (2,3-naphthalocyaninato)ruthenium [ ( ~B u )~-were characterized by UV/Vis, IR, and NMR measurements. MacRu] by thermal decomposition of (tBu)4MacRu(L)2 (L = Some years ago, we reported on the synthesis of pure (phthalocyaninato)ruthenium(II) (PcRu) by thermal decomposition of PcRu(DMSO)~ . 2 DMSO['l. Later, we developed a more convenient method for the preparation of pure PcRu via the corresponding bisisoquinoline complex PcRu(iqnl)2[2], which is readily available and can be thermally decomposed at 250°C with formation of pure PcRur3]. Recently, we also prepared (2,3-naphthalocyaninato)ruthenium(II) (2,3-NcRu) by thermal decomposition of the monomeric complex ~,Ruthenium complexes of the type MacRu(L)2 and [MacRu(L)], [Mac = Pc, 2,3-Nc; L = e.g. pyrazine (pyz), tetrazine (tz), or 1,4-diisocyanobenzene (dib)] are more stable than the well-studied iron complexes toward oxidation of the central metal atom. They show an increased stability due to the larger radius of the ruthenium ion.By peripheral attachment of bulky (e.g. tert-butyl) or long-chain groups (e.g. alkyl or alkoxy) to the macrocycles, transition metal phthalocyanine complexes RxPcM(L)2 and their bridged systems [R,PcM(L)], can be made soluble in common organic solvents, e.g. chloroform or t~l u e n e [~,~] . The tert-butyl group is especially suitable to increase the solubility of phthalocyanines in organic solvents [6]. Several attempts to prepare (tetra-tert-butylphtha1ocyaninato)ruthenium(I1) (tBu)4PcRu (1) have only led to impure (~Bu),PcRu(L),[~~. However, the crude compound can be used for the preparation of defined bisaxially coordinated monomers (tB~)~pcRu(L)* (L = e.g. pyridine, tert-butyl isocyanide) ['] and oligomers [(~BU>~PCRU(L)], (L = dib and me,dib) [']. For the coordination of weak bases such as pyrazine (pyz) or tetrazine (tz), which are important bridging ligands for e.g. intrinsic pure and non-coordinated (tBu),PcRu (1) is necessary because the ligands pyz and tz are not able to remove coordinated impurities in the process of preparation of [(tB~)~pcRu(L)],, L = pyz, tz, etc.In this paper we report on the synthesis and properties of pure (tBu),PcRu (1) and (tBu),-2,3-NcRu (2) which are potential precursors of soluble organic semiconductors. Results and DiscussionFor the synthesis of (tBu),PcRu (1) and (tBu)4-2,3-NcRu (2) by thermal decomposition of the corresponding bisaxially coordinated monomeric complexes (tB~)~Mac(L)2 attention must be paid to the fact that only the axial ligands and not the peripheral tBu substituents are split off. To attain a low decomposition temperature of the complexes (tBu),MacRu(L), (Mac = Pc, 2,3-Nc) some effects of the ligands L must be taken into consideration, e.g. electronic effects, which led us to use 3-chloropyridine (3-Clpy) because the chlorine atom in the 3-position should lower the coordination strength of the ligandr41. On the other hand, a back-bonding effect fr...
Four novel differently substituted 2,3-dicyanonaphthalenes (6-(hexyloxy)-2,3-dicyanonaphthalene (E), 5-(hexyloxy)-2,3-dicyanonaphthalene (11),6,7-bis(hexyloxy)-2,3-dicyanonaphthalene (171, and 5,8-diheptyl-2,3-dicyanonaphthalene (22)) and the respective peripherally substituted (bis(tertbutylisocyano)-2,3-naphthalocyaninato)iron(II) compounds 23-26 were synthesized and characterized.2,3-Naphthalocyanines have attracted much attention because of their potential use as semiconducting materials,lS2 in nonlinear optic^,^ as laser dyes,4 and in photodynamic the rap^.^ Due to intermolecular interactions between the macrocycles, peripherally unsubstituted metallophthalocyanines and also metallo-2,3-naphthalocyanines are practically insoluble in common organic solvents such as chloroform or toluene. Solubility, however, is necessary for many applications, e.g., thin film preparation by spin-coating and for the Langmuir-Blodgett technique. Although it has been shown that soluble compounds are formed by inserting side chains in the periphery of (phthalocyaninat0)metal complexes,' very little is known about the syntheses and properties of peripherally substituted 2,3-naphthalo~yanines.~,~ 2,3-Naphthalocyanines can be prepared by heating a mixture of 2,3-dicyanonaphthalene with the metal or the corresponding metal salt in an inert solvent.' To obtain information on the influence of alkyl and alkoxy chains on the solubility of 2,3-naphthalocyanines, we report here on the syntheses and characterization of four different heptyl-and hexyloxy-substituted 2,3-dicyanonaphthalenes, which were converted into the respective substituted (2,3-naphthalocyaninato)nickel complexes. Although these complexes were relatively soluble in organic solvents, their tendency to aggregate made the characterization by UV/vis and especially by NMR spectroscopy difficult, and they are not included in this paper. To prevent an aggregation we decided to synthesize the corresponding axially coordinated (bidtert-buty1isocyano)-2,3-naphthalocyaninato)iron compounds (&2,3-NcFe(t-Abstract published in Advance ACS Abstracts, November 15,1995. (1) (a) Hanack, M.; Datz, A.; Fay, R.; Fischer, K.; Keppeler, U.; Koch, J.; Metz, J.; Metzger, M.; Schneider, 0.; Schulze, H.-J. In Handbook ofconducting PoZymers; Skotheim, T., Ed.; Marcel Dekker: New York, 1986; p 133. (b) Schultz, H.; Lehmann, H.; Rein, M.; Hanack, M. (5) (a) Cuomo, V.; Jori, G.; Rihter, B.; Kenney, M. E.; Rodgers, M. A. J. Br. J . Cancer 1990,62, 966. (b) Yates, N. C.; Moan, J.; Western, A. J. Photochem. Photobiol., B 1990,4, 379. (c) Paquette, B.; Mi, H.; Langlois, R.; van Lier, J. E. Photochem. Photobiol. 1990, 51, 313. (d) Wiihrle, D.; Shopova, M.; Muller, S.; Milev, A. D.; Mantareva, V. N.; Krastev, K. K. J. Photochem. Photobiol., B 1.993,21,155. (e) Ford, W. E.; Rodgers, M. A. J.; Schechtman, L. A.; Sounik, J. R.; Rihter, B. D.; Kenney, M. E. Inorg. Chem. 1992,31, 3371. (6) Kovshev, E. I.; Puchnova, V. A.; Luk'yanets, E. A. Zh. Org. Khim. 1971, 7, 369. (7) Kopranenkov, V. N.; Makarova, E. A.; Luk'...
To obtain a more detailed insight into the structure of PcRu (1), an EXAFS investigation has been carried out on amorphous PcRu and compared with the bisubstituted PcRu(n-BuNH 2 ) 2 (2). From the obtained atomic distances around the metal center, it was possible to deduce detailed structural models for both compounds. For 1, the dimeric structure was confirmed; for 2, the EXAFS measurements led to an unusual structure in which both n-butylamine groups are located on one side of the PcRu ring.
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