Issue 22, 2011

Photophysical properties of Kuratowski-type coordination compounds [MIIZn4Cl4(Me2bta)6] (MII = Zn or Ru) featuring long-lived excited electronic states

Abstract

The syntheses of Kuratowski-type pentanuclear clusters featuring {MZn4Cl4} cores (MII = Ru or Zn) that incorporate triazolate ligands are described. The coordination compounds are characterized by single-crystal X-ray diffraction, X-ray powder diffraction (XRD), FTIR- and UV-vis spectroscopy. [RuIIZn4Cl4(Me2bta)6]·2DMF (Me2bta = 5,6-dimethyl-1,2,3-benzotriazolate) (1) crystallizes in the cubic system, while [Zn5Cl4(ta)6] (ta = 1,2,3-triazolate) (3) crystallizes in the tetragonal system. Both compounds feature structurally similar cluster topologies in which the central octahedrally coordinated metal ion is coordinated to six triazolate ligands. Each triazolate ligand is coordinated with two zinc ions3-bridging mode), leading altogether to a pentanuclear cluster of Td point group symmetry. Photophysical investigations reveal that compound [Zn5Cl4(Me2bta)6]·2DMF (2) shows a short-lived excited electronic state, which can be populated with high quantum yield. The isostructural compound [RuIIZn4Cl4(Me2bta)6]·2DMF (1), on the other hand, shows a long-lived photoexcited state, owing to an internal singlet to triplet conversion of the electronic states, as revealed by time-resolved fluorescence spectroscopy. Insights gained from these studies open up novel design strategies towards photocatalytically active metal–organic frameworks incorporating photoactive Kuratowski-type secondary building units such as MFU-4 (Metal–Organic Framework Ulm University-4).

Graphical abstract: Photophysical properties of Kuratowski-type coordination compounds [MIIZn4Cl4(Me2bta)6] (MII = Zn or Ru) featuring long-lived excited electronic states

Supplementary files

Article information

Article type
Paper
Submitted
12 Dec 2010
Accepted
25 Mar 2011
First published
03 May 2011

Dalton Trans., 2011,40, 5926-5938

Photophysical properties of Kuratowski-type coordination compounds [MIIZn4Cl4(Me2bta)6] (MII = Zn or Ru) featuring long-lived excited electronic states

Y. Liu, M. Grzywa, M. Tonigold, G. Sastre, T. Schüttrigkeit, N. S. Leeson and D. Volkmer, Dalton Trans., 2011, 40, 5926 DOI: 10.1039/C0DT01750G

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