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Titre du document / Document title

2-Aminopyrimidine directed self-assembly of zinc porphyrins containing bulky 3,5-di-tert-butylphenyl groups

Auteur(s) / Author(s)

BALABAN Teodor Silviu (1) ; GODDARD Richard (2) ; LINKE-SCHAETZEL Myriam (1) ; LEHN Jean-Marie (1 3) ;

Affiliation(s) du ou des auteurs / Author(s) Affiliation(s)

(1) Forschungzentrum Karlsruhe, Institute for Nanotechnology, Postfach 3640, 76021 Karlsruhe, ALLEMAGNE
(2) Max-Planck-lnstitut für Kohlenforschung, Kaiser-Wilkelm-Platz I, 45470 Mülheim an der Ruhr, ALLEMAGNE
(3) ISIS, Université Louis Pasteur, 8, rue Gaspard Monge, 67000 Strasbourg, FRANCE

Résumé / Abstract

The 2-aminopyrimidin-5-yl ligand is revealed to be a promising candidate for the construction of supramolecular porphyrin arrays with broad absorption bands for efficient light-harvesting. 10-Mono- and 10,20-di(2-aminopyrimidin-5-yl) derivatives of 5,15-bis(3,5-di-tert-butylphenyl)porphyrin have been synthesized in high yield. Their Zn(ll) salts show variable concentration and temperature-dependent UV/vis spectra in solution, consistent with supramolecular aggregation. Whereas the FAB mass spectra of the monosubsituted derivative in toluene suggest the formation of a tetramer at high concentrations and low temperatures (estimated association free enthalpy △H = 220 ± 10 kJ/mol), the larger splitting of the Sorret band (ca. 40 nm) in the variable temperature UV/vis spectra of the disubstituted bis(3,5-di-tert-butylphenyl)porphyrin is indicative of yet higher aggregates involving both 2-aminopyrimidin-5-yl groups. The tetrameric nature of the monosubsituted derivative is confirmed by X-ray analysis, which reveals that two of the 2-aminopyrimidin-5-yl groups are encapsulated by the aggregate and consequently are prevented from undergoing hydrogen bonding. NMR studies show there is no exhange of the 2-aminopyrimidin-5-yl groups, so the tetramer is rigid, which is confirmed by molecular modeling calculations. The tetramer formation is governed by π-π interactions, metal coordination, and hydrogen bonding. The di(2-aminopyrimidin-5-yl) derivative forms strongly scattering solutions, which upon standing form green flocculate precipitates, reminiscent of shaken suspensions of bacteriochlorophyll c.

Revue / Journal Title

Journal of the American Chemical Society    ISSN  0002-7863   CODEN JACSAT 

Source / Source

2003, vol. 125, no14, pp. 4233-4239 [7 page(s) (article)] (28 ref.)

Langue / Language

Anglais

Editeur / Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1879) (Revue)

Mots-clés anglais / English Keywords

Transition metal Complexes

;

Photoionization

;

Laser desorption

;

Matrix isolation

;

Mass spectrometry

;

Ultraviolet visible spectrometry

;

Thermodynamic parameter

;

Supramolecular structure

;

Molecular association

;

Molecular aggregation

;

Toluene

;

Organic solvent

;

Non aqueous solution

;

Nitrogen heterocycle

;

Organic ligand

;

Zinc Complexes

;

Metalloporphyrin

;

Experimental study

;

Mots-clés français / French Keywords

Métal transition Complexe

;

Spectrométrie MALDI

;

Pyrimidine(2-amino)

;

Porphyrine(10,20-bis[3,5-di-t-butylphényl])

;

Photoionisation

;

Désorption laser

;

Isolement matrice

;

Spectrométrie masse

;

Spectrométrie UV visible

;

Paramètre thermodynamique

;

Structure supramoléculaire

;

Association moléculaire

;

Agrégation moléculaire

;

Toluène

;

Solvant organique

;

Solution non aqueuse

;

Hétérocycle azote

;

Coordinat organique

;

Zinc Complexe

;

Porphyrine métallique

;

Etude expérimentale

;

Mots-clés espagnols / Spanish Keywords

Metal transición Complejo

;

Fotoionización

;

Desorción láser

;

Aislamiento matriz

;

Espectrometría masa

;

Espectrometría UV visible

;

Parámetro termodinámico

;

Estructura supramolecular

;

Asociación molecular

;

Agregación molecular

;

Tolueno

;

Solvente orgánico

;

Solución no acuosa

;

Heterociclo nitrógeno

;

Ligando orgánico

;

Zinc Complejo

;

Porfirina metálica

;

Estudio experimental

;

Localisation / Location

INIST-CNRS, Cote INIST : 551, 35400011795607.0500

Nº notice refdoc (ud4) : 14717535



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