Crystal structures of {1,1,1-tris-[(salicylaldimino)-meth-yl]ethane}-gallium as both a pyridine solvate and an aceto-nitrile 0.75-solvate and {1,1,1-tris[(salicylaldimino)-meth-yl]ethane}-indium di-chloro-methane solvate.

The sexa-dentate ligand 1,1,1-tris-[(salicyl-idene-amino)-meth-yl]ethane has been reported numerous times in its triply deprotonated form coordinated to transition metals and lanthanides, yet it has been rarely employed with main-group elements, including in substituted forms. Its structures with gallium and indium are reported as solvates, namely, ({[(2,2-bis-{[(2-oxido-benzyl-idene)amino-κ2 N,O]meth-yl}prop-yl)imino]-meth-yl}phenololato-κ2 N,O)gallium(III) pyridine monosolvate, [Ga(C26H24N3O3)]·C5H5N, the aceto-nitrile 0.75-solvate, [Ga(C26H24N3O3)]·0.75C2H3N, and ({[(2,2-bis-{[(2-oxido-benzyl-idene)amino-κ2 N,O]meth-yl}prop-yl)imino]-meth-yl}phenololato-κ2 N,O)indium(III) di-chloro-methane monosolvate, [In(C26H24N3O3)]·CH2Cl2. All three metal complexes are pseudo-octa-hedral and each structure contains multiple weak C-H⋯O and/or C-H⋯N inter-molecular hydrogen-bonding inter-actions. The syntheses and additional characterization in the forms of melting points, high-resolution mass spectra, infra-red (IR) spectra, and 1H and 13C NMR spectra are also reported.

MCD spectroscopy and TD-DFT calculations of low symmetry subnaphthalocyanine analogs.

Magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations are used to analyze the electronic structure and optical properties of low-symmetry subnaphthalocyanine analogs with AAB and ABB structures formed during mixed condensations of tetrafluorophthalonitrile and 2,3-naphthalenedicarbonitrile. The results demonstrate that trends observed in the properties of phthalocyanine analogs can be used to fine tune the optical properties so that the Q(0,0) bands lie in the red region, in a manner that does not significantly destabilize the highest occupied molecular orbital (HOMO) energy relative to that of the parent subphthalocyanine ligand. Attempts to study the spectroscopy of anion radical species proved unsuccessful, since they proved to be unstable.

Synthesis and characterization of lithium hemiporphyrazines.

The hemiporphyrazines comprise a broad class of phthalocyanine analogues where one or two of the diiminoisoindolene units are replaced with alternative rings, including pyridines, benzenes, and azoles. As a means to explore the fundamental metal chemistry of these macrocycles, we have prepared the first lithium complexes of three hemiporphyrazine variants: the common bis-pyridine ring, the bis-benzene macrocycle (also known as dicarbahemiporphyrazine), and the monobenzene variant (also known as benziphthalocyanine). The metal cation can be inserted via reaction of the free bases by using lithium bis(trimethylsilyl)amide, and the resulting products all form 1:1 complexes with protonation at the meso nitrogens providing charge balance. For the two carbahemiporphyrazines studied, the internal C-H bond remains intact upon metalation. Similar structures have been observed in the transition metal complexes of the carbaporphyrins. In addition, all three complexes are characterized by (7)Li solid state NMR and by cyclic voltammetry.

Low-coordinate transition-metal complexes of a carbon-substituted hemiporphyrazine.

The metallation of the core-modified phthalocyanine analogue dicarbahemiporphyrazine with manganese, iron, and cobalt results in the formation of low-coordinate metal(II) complexes. All three compounds are produced by the reaction of metal carbonyls with the free base macrocycle. As in many other carbaporphyrinoids, the internal C-H bonds remain intact upon metallation, resulting in the formation of two long-range agostic-type interactions. Each metal can thus be considered as a three-coordinate ion, where two inner isoindolene nitrogens and a single axial pyridine are bound to the metal. The manganese and cobalt complexes, Mn(dchp)py and Co(dchp)py, are nearly isostructural, but the iron complex, Fe(dchpH2)py, exhibits a reduction at an iminic double bond upon metallation.

Co(II) and Co(III) complexes of m-benziphthalocyanine.

The syntheses and structural elucidations of three different cobalt complexes of m-benziphthalocyanine are reported; both Co(II) and Co(III) complexes can be generated, and the ring undergoes partial oxidation upon metalation with Co(OAc)2x4H2O.

Chloro and hydroxo forms of a boron(III) subtriazaporphyrin macrocycle.

cis-3,4-Dicyano-3-hexene undergoes cyclotrimerization with BCl3 to form the new subtriazaporphyrin chloro[hexaethylsubtriazaporphyrinato]boron(III). The hydroxo derivative of this macrocycle has also been made, and the X-ray crystal structure of the hydroxy form was determined. Electronic absorption and magnetic circular dichroism spectra of the hydroxo monomer species were interpreted using time-dependent density functional theory calculations.

Synthesis of a quinone-functionalized macrocyclic ligand and the intense fluorescence of its zinc complex.

The redox-active quinone-functionalized macrocyclic ligand 1,4,14,17-tetrahydroxyhemiporphyrazine, H2hp(OH)4, has been synthesized and its zinc complex, [Zn(hp(OH)4)(py)], found to exhibit intense fluorescence.

An optically-active subphthalocyanine dimer.

A subphthalocyanine (SubPc) dimer linked by racemic 1,1'-binaphth-2,2'-dioxy (BINOL), 1, has been synthesized and characterized by 1- and 2-D 1H NMR, high resolution mass spectrometry (FAB), X-ray crystallography and electronic absorption spectroscopy. Additionally, the dimer derived from optically-active (R)-(+)-BINOL, 2, has been made and studied using CD and MCD spectroscopies.