808111-48-0Relevant academic research and scientific papers
(Fluoren-9-ylidene)methanedithiolato complexes of gold: Synthesis, luminescence, and charge-transfer adducts
Vicente, Jose,Gonzalez-Herrero, Pablo,Garcia-Sanchez, Yolanda,Jones, Peter G.,Bardaji, Manuel
, p. 7516 - 7531 (2008/10/09)
Piperidinium 9H-fluorene-9-carbodithioate and its 2,7-di-tert-butyl- substituted analogue [(pipH){S2CCH(C12H6R 2-2,7)}, R = H (1a), t-Bu (1b)] and 2,7-bis(octyloxy)-9H-fluorene-9- carbodithioic acid [HS2CCH(C12H6(OC 8H17)2-2,7), 2] and its tautomer [2,7-bis(octyloxy)fluoren-9-ylidene]methanedithiol [(HS)2C=C(C 12H6(OC8H17)2-2,7), 3] were employed for the preparation of gold complexes with the (fluoren-9-ylidene)methanedithiolato ligand and its substituted analogues. The gold(I) compounds Q2[Au2{μ-K2-S,S-S 2C=C12H6R2-2,7)}2], where Q+ = PPN+ or Pr4N+ for R = H (Q24a) or Q+ = Pr4N+ for R = OC 8H17 [(Pr4N)24c], were synthesized by reacting Q[AuCl2] with 1a or 2 (1:1) and excess piperidine or diethylamine. Complexes of the type [{Au(PR′3)} 2{,u-κ2-S,S-S2C=C(C12H 6R2-2,7)}2] with R = H and R′ = Me (5a), Et (5b), Ph (5c), and Cy (5d) or R = t-Bu and R′ = Me (5e), Et (5f), Ph (5g), and Cy (5h) were obtained by reacting [AuCl(PR'3)] with 1a,b (1:2) and piperidine. The reactions of 1a,b or 2 with Q[AuCl4] (2:1) and piperidine or diethylamine gave Q[Au{κ2-S,S-S 2C=C(C12H6R2-2,7)}2] with Q+ = PPN+ for R = H [(PPN)-6a], Q+ = PPN + or Bu4N+ for R = t-Bu (Q6b), and Q + = Bu4N+ for R = OC8H17 [(Bu4N)6c]. Complexes Q6a-c reacted with excess triflic acid to give [Au{κ2-S,S-S2C=C(C12H6R 2-2,7)}{κ2-S,S-S2CCH(C12H 6R2-2,7)}] [R = H (7a), t-Bu (7b), OC8H 17 (7c)]. By reaction of (Bu4N)6b with PhlCl2 (1:1) the complex Bu4N[AuCl2{κ2-S,S- S2C= C(C12H6(t-Bu)2-2,7)}] [(Bu 4N)8b] was obtained. The dithioato complexes [Au{SC(S)CH(C 12H8)}{PCy3)] (9) and [Aun(S 2-CCH(C12H8)}n] (10) were obtained from the reactions of 1a with [AuCl(PCy3)] or [AuCl(SMe 2)], respectively (1:1), in the absence of a base. Charge-transfer adducts of general composition Q[Au{κ2-S,S-S 2C=C(C12H6R2-2,7)}2]· 1.5TCNQ·xCH2Cl2 [Q+ = PPN+, R = H, x = 0 (11a); Q+ = PPN+, R = t-Bu, x = 2 (11b); Q+ = Bu4N+, R = OC8H17, x = 0 (11c)] were obtained from Q6a-c and TCNQ (1:2). The crystal structures of 5c·THF, 5e·2/3CH2Cl2, 5g·CH 2Cl2, (PPN)6a·2Me2CO, and 11b were solved by X-ray diffraction studies. All the gold(I) complexes here described are photoluminescent at 77 K, and their emissions can be generally ascribed to LMMCT (Q24a,c, 5a-h, 10) or LMCT (9) excited states.
