Dinuclear gold(I) dithiophosphonate complexes: synthesis, luminescent properties, and X-ray crystal structures of [AuS2PR(OR')]2 (R = Ph, R' = C5H9; R = 4-C6H4OMe, R' = (1S,5R,2S)-(-)-Menthyl; R = Fc, R' = (CH2)2O(CH2)2OMe).

Resumen

2,4-Diaryl- and 2,4-diferrocenyl-1,3-dithiadiphosphetane disulfide dimers (RP(S)S)2 (R = Ph (1a), 4-C 6H 4OMe (1b), FeC 10H 9 (Fc) (1c)) react with a variety of alcohols, silanols, and trialkylsilyl alcohols to form new dithiophosphonic acids in a facile manner. Their corresponding salts react with chlorogold(I) complexes in THF to produce dinuclear gold(I) dithiophosphonate complexes of the type [AuS 2PR(OR′)] 2 in satisfactory yield. The asymmetrical nature of the ligands allows for the gold complexes to form two isomers (cis and trans) as verified by solution 1H and 31P{ 1H} NMR studies. The X-ray crystal structures of [AuS 2PR(OR′)] 2 (R = Ph, R′ = C 5H 9 (2); R = 4-C 6H 4OMe, R′ = (1S,5R,2S)-(-)-menthyl (3); R = Fc, R′ = (CH 2) 2O(CH 2) 2OMe (4)) have been determined. In all cases only the trans isomer is obtained, consistent with solid state 31P NMR data obtained for the bulk powder of 3. Crystallographic data for 2 (213 K): orthorhombic, Ibam, a = 12.434(5) Å, b = 19.029(9) Å, c = 11.760(4) Å, V = 2782(2) Å 3, Z = 4. Data for 3 (293 K): monoclinic, P2 1, a = 7.288(2) Å, b = 12.676(3) Å, c = 21.826(4) A, β = 92.04(3)°, V = 92.04(3)°, V = 2015.0(7) Å 3, Z = 2. Data for 4 (213 K): monoclinic, P2 1/n, a = 11.8564(7) Å, b = 22.483(1) Å, c = 27.840(2) Å, β = 91.121(1)° V = 7419.8(8) Å 3, Z = 8. Moreover, 1a-c react with [Au 2(dppm)Cl 2] to form new heterobridged trithiophosphonate complexes of the type [Au 2(dppm)(S 2P(S)R)] (R = Fc (12)). The luminescence properties of several structurally characterized complexes have been investigated. Each of the title compounds luminesces at 77 K. The results indicate that the nature of Au...Au interactions in the solid state has a profound influence on the optical properties of these complexes.