Suprasupermolecules with Novel Properties: Metallodendrimers.

Subphthalocyanines: singular nonplanar aromatic compounds-synthesis, reactivity, and physical properties.

7.1. Synthesis 306 7.2. Spectroscopic and Redox Properties 307 7.2.1. Optical Spectroscopy 307 7.2.2. Redox Properties 310 7.2.3. Other Characterization Methods 312 8. seco-Porphyrazines 312 8.1. Synthesis 312 8.2. Spectroscopic and Redox Properties 312 8.2.1. Optical Spectroscopy 312 8.2.2. Redox Properties 313 8.2.3. Other Characterization Methods 313 9. Conclusions 313 10. Abbreviations 314 11. Acknowledgments 314 12. References 314

Low Symmetry Phthalocyanines and Their Analogues

Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation, we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and f...

Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines

Transition metal complexes in which hydrocarbons serve as σ,σ-, σ,π- or π,π-bound bridging ligands are currently of great interest. This review presents efficient and directed syntheses for such compounds, which often have very aesthetic structures. These reactions are among the most important reaction types in modern organometallic chemistry. They can be a useful aid for the synthesis of tailor-made compounds, for example, for models of catalytic processes and, specifically, for the construction of heterometallic compounds. We will discuss reactions of electrophilic complexes with nucleophilic ones, numerous transformations of (functionalized) hydrocarbons with metal complexes, the currently very topical complexes with bridging acetylide and carbide ligands, and organometallic polymers, which can be expected to have interesting and novel materials properties. Chisholm1 has described the importance of these complexes as follows: “Central to the development of polynuclear and cluster chemistry are bridging ligands and central to organometallic chemistry are metal–carbon bonds. Thus bridging ligands hold a pivotal role ins the development of Binuclear and polynuclear organometallic chemistry”.

Methods for the Synthesis of μ‐Hydrocarbon Transition Metal Complexes without Metal–Metal Bonds

Metal-free phthalocyanines and metal phthalocyaninates (M = Ni, Cu, Co or Zn) carrying eight alkylthio-groups on peripheral positions have been synthesised from 4,5-bis(alkylthio)phthalonitrile and 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) or the corresponding anhydrous metal salt [NiCl2, CuCl, CoCl2 or Zn(O2CMe)2]. The resulting compounds reacted with silver(I) or palladium(II) salts to form complexes with a phthalocyanine:metal ratio of 1 : 4. Spectrophotochemical investigation of these reactions revealed that complexation with AgI results in aggregation, while the addition of PdII destroys the aggregation and yields a new Q band at 720 nm.

Octakis(alkylthio)-substituted phthalocyanines and their interactions with silver(I) and palladium(II) ions

Metal phthalocyanines (M=Cu, Ni, Co, SnCl 2 ) 3-6 containing four 14-membered tetraaza macrocycles have been prepared. Detosylation of the aza functions has provided donor sites for binding four Ni 2+ ions giving a pentanuclear complex which is extremely soluble in polar solvents. The mass spectrum of the [hexadecakis(N-p-tosyl)-tetrakis-macrocycle-phthalocyaninato]copper(II) 3 is described

Synthesis and Characterization of Phthalocyanines Containing Four 14-Membered Tetraaza Macrocycles

Unsymmetrical phthalocanines (5–7) with a single macrocyclic substituent are synthesized by the reaction of the boron complex of phthalonitrile (1) with the iminoisoindoline derivatives 2–4 of macrocyclic compounds, i.e. 15-crown-5, monoaza-15-crown-5, and tetraazacyclotetradecane. The monomacrocycle-substituted phthalocyanines are less soluble than the tetra-substituted one.

Unsymmetrical phthalocyanines with a single macrocyclic substituent

Cyclotrimerization of 4,5-bis(hexylthio)phthalodinitrile (1) in 1-chloronaphthalene in the presence of BCl 3 leads to the subphthalocyanine 4. Unsymmetrical phthalocyanines (5, 6) with six alkylthio substituents on three of the benzenoid units are synthesized by the reaction of 4 with an diiminoisoindoline derivative (R'=H or NO 2 ). These extremely soluble compounds are characterized by IR, 1 H- and 13 C-NMR as well as UV/Vis spectra

Özer Bekaroǧlu

Papers

Octakis(alkylthio)-substituted phthalocyanines and their interactions with silver(I) and palladium(II) ions

Synthesis and Characterization of Phthalocyanines Containing Four 14-Membered Tetraaza Macrocycles

Unsymmetrical phthalocyanines with a single macrocyclic substituent

Hexakis(alkylthio)-substituted unsymmetrical phthalocyanines

Electrochemical and spectral properties of octakis(hexylthio)-substituted phthalocyanines