3D Au-Ag heterometallic supramolecular cage: triplet capture by heavy atom effect

Laura Rodríguez, João C. Lima, Montserrat Ferrer, Oriol Rossell, Marianne Engeser

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The synthesis of a new 3D metallo-cage is obtained by means of the self-assembly reaction between the gold derivative [(triphos)(AuC 6F 4py) 3] (triphos = 1,1,1- tris(diphenylphosphanylmethyl)ethane) and AgOTf in a 2:3 ratio. Several spectroscopic and spectrofluorimetric techniques and mass spectrometry have been used for the characterization of the supramolecule. MM calculations have been also important in order to optimize the geometry of the structure and postulate its ability to act as host in molecular recognition processes by means of its empty inner cavity. Changes on the emission spectra of the guest molecules naphthalene, methylsalicylate and 8-hydroxyquinoline showed the establishment of interactions between these molecules and the cage. A 1:2 cage:naphthalene adduct has been obtained while a 2:3 ratio has been observed for methylsalicylate and 8-hydroxyquinoline. Interestingly, the large number of metal atoms of the host has been observed to induce intersystem crossing of the organic molecules. Emission spectra at 77 K together with lifetime measurements are a definitive proof for the assignment of the triplet origin for the observed guest luminescence when trapped by the host.

Original languageEnglish
Pages (from-to)195-202
Number of pages8
JournalInorganica Chimica Acta
Volume381
Issue number1
DOIs
Publication statusPublished - 15 Feb 2012

Fingerprint

Oxyquinoline
Naphthalene
naphthalene
Atoms
Molecules
emission spectra
atoms
molecules
Molecular recognition
Ethane
axioms
Gold
ethane
Self assembly
adducts
Mass spectrometry
Luminescence
self assembly
mass spectroscopy
Metals

Keywords

  • Metallo-cage
  • Molecular recognition
  • Phosphorescence
  • Self-assembly
  • Triplet

Cite this

Rodríguez, Laura ; Lima, João C. ; Ferrer, Montserrat ; Rossell, Oriol ; Engeser, Marianne. / 3D Au-Ag heterometallic supramolecular cage: triplet capture by heavy atom effect. In: Inorganica Chimica Acta. 2012 ; Vol. 381, No. 1. pp. 195-202.
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3D Au-Ag heterometallic supramolecular cage: triplet capture by heavy atom effect. / Rodríguez, Laura; Lima, João C.; Ferrer, Montserrat; Rossell, Oriol; Engeser, Marianne.

In: Inorganica Chimica Acta, Vol. 381, No. 1, 15.02.2012, p. 195-202.

Research output: Contribution to journalArticle

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AU - Lima, João C.

AU - Ferrer, Montserrat

AU - Rossell, Oriol

AU - Engeser, Marianne

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AB - The synthesis of a new 3D metallo-cage is obtained by means of the self-assembly reaction between the gold derivative [(triphos)(AuC 6F 4py) 3] (triphos = 1,1,1- tris(diphenylphosphanylmethyl)ethane) and AgOTf in a 2:3 ratio. Several spectroscopic and spectrofluorimetric techniques and mass spectrometry have been used for the characterization of the supramolecule. MM calculations have been also important in order to optimize the geometry of the structure and postulate its ability to act as host in molecular recognition processes by means of its empty inner cavity. Changes on the emission spectra of the guest molecules naphthalene, methylsalicylate and 8-hydroxyquinoline showed the establishment of interactions between these molecules and the cage. A 1:2 cage:naphthalene adduct has been obtained while a 2:3 ratio has been observed for methylsalicylate and 8-hydroxyquinoline. Interestingly, the large number of metal atoms of the host has been observed to induce intersystem crossing of the organic molecules. Emission spectra at 77 K together with lifetime measurements are a definitive proof for the assignment of the triplet origin for the observed guest luminescence when trapped by the host.

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