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Vapochromic Complexes

E.J. Fernández, J.M. López de Luzuriaga, M. Monge, M.E. Olmos, J. Pérez, A. Laguna

Closed-shell interactions occur mainly for some heavy late transition metals and main-group elements. In fact, these are dispersion forces reinforced by relativistic effects and by ionic components, of which the former are maximized in heteronuclear interactions. Heteronuclear compounds containing gold(I) and group-11, -12, and -13 metals display d 10 -d 10 or d 10 -s 2 closed-shell interactions of intermediate strength relative to the homonuclear metal-metal inter­actions. The number of examples of gold(I)-gold(I) contacts is large, but representatives of heteronuclear gold(I)-metal contacts are still scarce. There are two general types of derivatives displaying short gold-metal distances -- those with bridging ligands and those that are unbridged, of which the latter are always the more indicative of the presence of a real bond. Derivatives featuring unsupported gold-metal bonds have been obtained mainly through reactions between basic gold(I) complexes and acid complexes, and also by encapsulation of metal centers in metallocryptands. Most derivatives with supported gold-metal bonds have been synthesized by use of C-donor ligands or ambidentate ligands. The gold-metal contacts dramatically affect the conformations and the aggregation of the molecules, and also their optical properties. Some of these derivatives are, in fact, intensely luminescent [1].

The picture shows a disc that contains a suspension of the complex [(C 6 F 5 ) 2 Au{µ-Ag(OClO 3 )}Au(C 6 F 5 ) 2 ] (solid) under ultraviolet light. The border of the disc is cooled with liquid nitrogen to a temperature close to 77 K and the centre of the disc is at room temperature. The luminescence and the colour of the complex changes from red (near 77 K), through orange and yellow, to green (room temperature) [2].

The complex {Tl[Au(C 6 Cl 5 ) 2 ]} n , displays a vapochromic behavior with reversible color changes when the solid is exposed to a variety of organic vapors. Acetone, acetonitrile, triethyl­amine, acetylacetone, tetrahydrothiophene (THT), 2-fluoropyridine, tetrahydrofuran (THF), and pyridine vapors (see Figure 2) have been used. The color changes back to that of the starting material upon heating to 100 °C over a period that requires from a few seconds for acetone to 10 min for pyridine. In all cases, the process is found to be completely reversible with no detectable degradation of the starting material after 10 exposure/heating cycles. The exchange of color is even deeper under UV light, and the substances display a strong luminescence under these conditions.

Figure 2. Powder samples of {Tl[Au(C 6 Cl 5 ) 2 ]} n , deposited on filter paper and exposed to selected organic vapors: (1) 2-flouropyridine, (2) THF, (3) acetone, (4) acetylacetone, (5) acetonitrile, (6) pyridine, (7) triethylamine, (8) THT.

Principal publication

E.J. Fernández, J.M. López de Luzuriaga, M. Monge, M.E. Olmos. J. Pérez, A. Laguna, A.A. Mohamed and J.P. Fackler. J. Am. Chem. Soc. , 2003 125, 2022.

Acknowledgements

This work was supported by the Dirección General de Investigación (BQU2001-2409)

References

  • [1] M. Bardají and A. Laguna. Eur. J. Inorg. Chem., 2003, 3069.
  • [2] E.J. Fernández, M.C. Gimeno, A. Laguna, J.M. López de Luzuriaga, M. Monge, P. Pyykkö and D. Sundholm. J. Am. Chem. Soc. , 2000, 122, 7287.

 

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