Macrocycles characterized

Phthalocyanines are macrocycles characterized by an extensive 2D planar and centrosymmetric 18 7i-electron system. For this reason they have been widely investigated as third-order NLO materials and in particular as potential materials for OL some recent reviews have appeared in this specific field [163, 185, 186]. Only in the last decade have the second-order NLO properties been investigated and some of the reviews reported above describe the first significant results [164, 185]. Hereafter, we will highlight the must relevant results achieved since 2003 in the field of phthalocyanines showing second-order NLO properties. 

Costamagna, J., J. Canales, J. Vargas, M. CamaUi, F. Caruso, and E. Rivarola (1993). Precursors of aza-macrocycles—characterization of substituted phenanthrolines and related bases—crystal and molecular-structure of dichloro-di-n-butyl(2, 2, 6, 6 -bip5uimidine)-tin(lV). PureAppl. Chem. 65(7), 1521-1526. 

Quite a number of mixed sulfur-nitrogen macrocycles have been prepared, but these have largely been by the methods outlined in Chaps. 4 and 5 for the respective heteroatoms. An alternative method, involves the formation of a Schiff base, followed by reduction to the fully saturated system, if desired. An interesting example of the Schiff base formation is found in the reaction formulated in (6.12). Dialdehyde 14 is added to ethylenediamine in a solution containing ferrous ions. Although fully characterized, the yield for the reaction is not recorded. To avoid confusion with the original literature, we note the claim that the dialdehyde [14] was readily prepared in good yield by reaction of the disodium salt of 3-thiapentane-l, 5-diol . The latter must be the dithiol rather than the diol. 

This compound has been investigated by several groups,379- 384 but due to its practical insolubility it has not been fully characterized. Another approach to obtain phthalocyanine network polymers is with the use of crown ethers385 or other groups like di oxy -para-p h enyle n e3 8 6 as bridging units between the macrocycles. Some attempts to obtain metal phthalocyanine substructures arranged as ladder polymers have also been proposed (see below).344... 

Mononuclear complexes of palladium and platinum in the +3 oxidation state have only recently been unequivocally characterized [157]. The major advance has come in complexes with macrocyclic ligands such as 1,4,7-trithiacyclononane (ttcn) and 1,4,7-triazacyclononane (tacn) (Figure 3.96). 

Compounds 139 are tris(oximehydrazone) derivatives with an iron(ll) ion in the center of the cavity [230]. Compound 140 (Fig. 38) has been known for 30 years [231, 232] and was prepared from a tris(2-aldoximo-6-pyridyl)phos-phine that is capped by a BF unit to encapsulate cobalt(ll), zinc(ll), nickel(ll), and iron(II). All four macrocyclic complexes were characterized later by a comparative X-ray crystallographic study [233-236]. 

All cyclic compounds of types 83-88 have been characterized by their diagnostically simple and C-NMR spectra. Some general regularities can be observed, namely, a small but steady upfield shift in the C-NMR spectra of the carbon signals of the polyacetylenic macrocycle with increasing ring sizes. 

With sp bond angles calculated to be around 162°, macrocycle 131 would be highly strained and was therefore expected to be quite reactive [79]. The octa-cobalt complex 132, on the other hand, should be readily isolable. Indeed, 132 was prepared easily from 133 in five steps, and was isolated as stable, deep maroon crystals (Scheme 30). All spectroscopic data supported formation of the strain-free dimeric structure. Unfortunately, all attempts to liberate 132 from the cobalt units led only to insoluble materials. Diederich et al. observed similar problems when trying to prepare the cyclocarbons [5c]. Whether the failure to prepare these two classes of macrocycles is due to the extreme reactivity of the distorted polyyne moiety or to the lack of a viable synthetic route is not certain. Thus, isolation and characterization of smaller bent hexatriyne- and octatetrayne-containing systems is an important goal that should help answer these questions. 

Goff (54) synthesized an Fe(III) porphyrin with a 2-hydroxyphenyl group at one meso position (35, Fig. 12a). Under basic conditions, the system spontaneously dimerizes due to phenolate-Fe(III) coordination. The complex is very stable and was isolated and fully characterized. In the solid state, the X-ray crystal structure confirmed the structure of the assembly as a macrocyclic head-to-tail dimer with two intermolecu-... 

Our most recent work with B megapotamica has been with the isolation of large quantities of baccharinoids from a 1800 Kg collection. The workup of the crude extract (ca. 30 Kg of black tarry material) of this plant material was conducted by Dr. Fred Boettner of Polyscience, Inc. This near Herculean task required tremendous quantities of solvents, column packings and time to complete. An outline of the fractionation scheme is presented in Figure 2. Fractions F6-F11 contain a large number of baccharinoids. To date, we have characterized over twenty macrocyclic trichothecenes found in B mega-... 

The fe-Ir1 complex (344) of the selena sapphyrin ligand has been synthesized and characterized by X-ray diffraction studies.551 The pairs of bound N atoms in (344) are bent towards the Ir1 centers, and the respective pyrrole rings are twisted from the macrocyclic plane. The coordination geometry around the Ir is close to square-planar, and the Ir Ir distance is 4.233 A. The Se center is not involved in bonding to the Ir centers. 

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