Large metal ion-centered template reactions. Chemical and spectral studies of the "superphthalocyanine" dioxocyclopentakis(1-iminoisoindolinato)uranium(VI) and its derivatives

Tobin J Marks, Djordje R. Stojakovic

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Abstract

This paper reports on chemical and spectral studies of the macrocyclic uranyl complexes dioxocyclopentakis(1-iminoisoindolinato)uranium(VI), SPcUO2, and dioxocyclopentakis(1-imino-5-methylisoindolinato)uranium(VI), Me5SPcUO2. These expanded, five-subunit analogues of phthalocyanines were synthesized in template reactions from uranyl salts and the corresponding phthalonitriles. The conditions for a high-yield synthesis are critical and include a polar solvent (e.g., dimethyl-formamide), high temperatures, and strict exclusion of water. Phthalocyanine, PcH2, is a side product of the reaction with the source of protons being the solvent. Attempts to displace the uranyl ion from SPcUO2 with acids or other metal ions (Mn+) invariably result in macrocycle contraction to produce PcH2 or PcMn-2 and phthalonitrile. 1H NMR studies reveal the five-subunit macrocycle to be stereochemically dynamic. The analysis of ring current induced 1H NMR shifts indicates considerably reduced π electron delocalization in SPcUO2 compared to PcM derivatives. The electronic spectrum of SPcUO2 exhibits strong absorption maxima at 4240 and 9140 Å. With the aid of Pariser-Parr-Pople SCFLCAOCl π electron molecular orbital calculations, the electronic structure of the macrocycle and the origin of the spectral transitions can be shown to be closely analogous to phthalocyanine systems. Many of the chemical and spectral properties of SPcUO2 and Me5SPcUO2 reflect the severe buckling and strain within the macrocyclic ligand.

Original languageEnglish
Pages (from-to)1695-1705
Number of pages11
JournalJournal of the American Chemical Society
Volume100
Issue number6
Publication statusPublished - 1978

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Uranium
Heavy ions
Metal ions
Metals
Nuclear magnetic resonance
Ions
Derivatives
Orbital calculations
Electrons
Induced currents
Dimethylformamide
Molecular orbitals
Buckling
Electronic structure
Protons
Ligands
Salts
Acids
Water
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Large metal ion-centered template reactions. Chemical and spectral studies of the {"}superphthalocyanine{"} dioxocyclopentakis(1-iminoisoindolinato)uranium(VI) and its derivatives",
abstract = "This paper reports on chemical and spectral studies of the macrocyclic uranyl complexes dioxocyclopentakis(1-iminoisoindolinato)uranium(VI), SPcUO2, and dioxocyclopentakis(1-imino-5-methylisoindolinato)uranium(VI), Me5SPcUO2. These expanded, five-subunit analogues of phthalocyanines were synthesized in template reactions from uranyl salts and the corresponding phthalonitriles. The conditions for a high-yield synthesis are critical and include a polar solvent (e.g., dimethyl-formamide), high temperatures, and strict exclusion of water. Phthalocyanine, PcH2, is a side product of the reaction with the source of protons being the solvent. Attempts to displace the uranyl ion from SPcUO2 with acids or other metal ions (Mn+) invariably result in macrocycle contraction to produce PcH2 or PcMn-2 and phthalonitrile. 1H NMR studies reveal the five-subunit macrocycle to be stereochemically dynamic. The analysis of ring current induced 1H NMR shifts indicates considerably reduced π electron delocalization in SPcUO2 compared to PcM derivatives. The electronic spectrum of SPcUO2 exhibits strong absorption maxima at 4240 and 9140 {\AA}. With the aid of Pariser-Parr-Pople SCFLCAOCl π electron molecular orbital calculations, the electronic structure of the macrocycle and the origin of the spectral transitions can be shown to be closely analogous to phthalocyanine systems. Many of the chemical and spectral properties of SPcUO2 and Me5SPcUO2 reflect the severe buckling and strain within the macrocyclic ligand.",
author = "Marks, {Tobin J} and Stojakovic, {Djordje R.}",
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T1 - Large metal ion-centered template reactions. Chemical and spectral studies of the "superphthalocyanine" dioxocyclopentakis(1-iminoisoindolinato)uranium(VI) and its derivatives

AU - Marks, Tobin J

AU - Stojakovic, Djordje R.

PY - 1978

Y1 - 1978

N2 - This paper reports on chemical and spectral studies of the macrocyclic uranyl complexes dioxocyclopentakis(1-iminoisoindolinato)uranium(VI), SPcUO2, and dioxocyclopentakis(1-imino-5-methylisoindolinato)uranium(VI), Me5SPcUO2. These expanded, five-subunit analogues of phthalocyanines were synthesized in template reactions from uranyl salts and the corresponding phthalonitriles. The conditions for a high-yield synthesis are critical and include a polar solvent (e.g., dimethyl-formamide), high temperatures, and strict exclusion of water. Phthalocyanine, PcH2, is a side product of the reaction with the source of protons being the solvent. Attempts to displace the uranyl ion from SPcUO2 with acids or other metal ions (Mn+) invariably result in macrocycle contraction to produce PcH2 or PcMn-2 and phthalonitrile. 1H NMR studies reveal the five-subunit macrocycle to be stereochemically dynamic. The analysis of ring current induced 1H NMR shifts indicates considerably reduced π electron delocalization in SPcUO2 compared to PcM derivatives. The electronic spectrum of SPcUO2 exhibits strong absorption maxima at 4240 and 9140 Å. With the aid of Pariser-Parr-Pople SCFLCAOCl π electron molecular orbital calculations, the electronic structure of the macrocycle and the origin of the spectral transitions can be shown to be closely analogous to phthalocyanine systems. Many of the chemical and spectral properties of SPcUO2 and Me5SPcUO2 reflect the severe buckling and strain within the macrocyclic ligand.

AB - This paper reports on chemical and spectral studies of the macrocyclic uranyl complexes dioxocyclopentakis(1-iminoisoindolinato)uranium(VI), SPcUO2, and dioxocyclopentakis(1-imino-5-methylisoindolinato)uranium(VI), Me5SPcUO2. These expanded, five-subunit analogues of phthalocyanines were synthesized in template reactions from uranyl salts and the corresponding phthalonitriles. The conditions for a high-yield synthesis are critical and include a polar solvent (e.g., dimethyl-formamide), high temperatures, and strict exclusion of water. Phthalocyanine, PcH2, is a side product of the reaction with the source of protons being the solvent. Attempts to displace the uranyl ion from SPcUO2 with acids or other metal ions (Mn+) invariably result in macrocycle contraction to produce PcH2 or PcMn-2 and phthalonitrile. 1H NMR studies reveal the five-subunit macrocycle to be stereochemically dynamic. The analysis of ring current induced 1H NMR shifts indicates considerably reduced π electron delocalization in SPcUO2 compared to PcM derivatives. The electronic spectrum of SPcUO2 exhibits strong absorption maxima at 4240 and 9140 Å. With the aid of Pariser-Parr-Pople SCFLCAOCl π electron molecular orbital calculations, the electronic structure of the macrocycle and the origin of the spectral transitions can be shown to be closely analogous to phthalocyanine systems. Many of the chemical and spectral properties of SPcUO2 and Me5SPcUO2 reflect the severe buckling and strain within the macrocyclic ligand.

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