Gold-Thallium Derivatives

FIGURE 14. The polymeric complex [CuAu(C6F5)2(MeCN)( j,2-C4H4N2)]K- 

As described above, among the several closed-shell metal ions that form luminescent supramolecular entities with gold, thallium(I) forms the most numerous examples. While aurophilic attractions can be considered the upper extreme of the metallophilic interactions (with values up to 46 kJ mol-1), intermetallic contacts involving T1(I) centers appear as the weakest ones (even 20 kJ mol-1),46 which is explained by the enhancement of the Au---Au interactions and the weakening of the Van der Waals attractions between the s2 metal atoms produced by the relativistic effects.47 Nevertheless, the complexes in which this interaction appears are surprisingly stable, with additional electrostatic, packing forces, or the ligand architecture, responsible for this fact. 

For instance, the strength of the Au(I) T1(I) contacts in extended linear chains with an average metal-metal separation of 3.03 A is estimated at 276 kJ mol-1, of which 80% consists on ionic interaction.48 Consequently, the rationalization of the bonding in these species still remains as a challenge for synthetic and theoretical chemists. 

Another challenge is now to tune the emissive properties of these compounds, which implies the study of all the factors that modify them, such as the intemetallic distance, the coordination number and geometry around the metal centers—which in the case of T1(I) is variable49—or the donor characteristics of the ligands. 

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The complexes exhibited different behavior in solution. The gold-thallium derivative showed a shift of the emission to 536 nm when the measurement was carried out in frozen solution. This was explained by a higher aggregation of [Aull(MTP)2] units in the solid state compared to the situation in solution. In the case of the Au-Pb compound, the emission spectrum showed a strong dependence on the aggregation state and temperature. Thus, the emission band in TH F solution, which appeared at 555 nm (298 K) (x = 57 ns), was shifted to 480 nm in frozen solution (x = 2.3 ps) or appeared at 752 nm in solid state (x = 22 ns). As with the thallium complex, the shift to high energy in solution may have been related to the polymeric structure of the complex in the solid state that was not reproduced in solution. 

The electron rich aurate [Au(C6F5)2] also reacts with thallium salts in the presence of a ligand to give extended unsupported gold-thallium linear chain derivatives. The first example... 

It is interesting that in contrast to other gold thallium chains, the pen-tafluorophenyl derivative (Fig. 17a) exhibits a nonalternating sequence of... 

C6C15) with dimethylsulfoxide (DMSO), which leads to the synthesis of [Tl2 Au(C6F5)2 2 p-DMSO 3] or [Tl2 Au(C6Cl5)2 2 h-DMSO 2]ra, respectively.62 The crystal structure of the complex with fluorine shows a monodimensional polymer formed by repetition of [Au--Tl(p-0 = SMe2)3Tl] units, with gold-thallium interactions of 3.2225(6)-3.5182(8), while the pentachlorophenyl derivative contains two bridging DMSO molecules and an additional [Au(C6Cl5)2] anion. In addition, a thallium-thallium interaction of 3.7562(6) A appears in the latter (Fig. 21). 

Thallium(i) Derivatives of Nickel, Palladium, Platinum, and Gold Coordination Complexes 395... 

Its absorption spectrum shows one band at 320 nm (e = 2900 M 1cm 1), assigned to the cti - ct2 transition localized in the Au-Tl moiety. The emission spectrum in the solid state at 77 K shows a band at 602 nm, which is attributable to a transition between orbitals that appear as a result of the metal-metal interaction. In this sense, Fenske-Hall molecular orbital calculations indicate that the ground state is the result of the mixing of the empty 6s and 6pz orbitals of gold(I) with the filled 6,v and the empty 6pz orbitals of thallium(I). In frozen solution, this derivative shows a shift of the emission to 536 nm, which has been explained by a higher aggregation of [AuT1(MTP)2] units in the solid state if compared to the situation in solution. 

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