Phosphorescent Excited State of [Au₂{(Ph₂Sb)₂O}₃]²⁺:  Jahn−Teller Distortion at Only One Gold(I) Center

Abstract

Dinuclear three-coordinate Au(I) complex [Au2{(Ph2Sb)2O}3](ClO4)2 1 displays an interesting phosphorescent behavior in which a large Stokes' shift is observed. Ab initio calculations show that the main distortion for the first triplet excited state, which is responsible for the luminescence behavior of complex 1, is a Jahn-Teller distortion for only one of the Au(I) centers together with a gold-gold distance shortening. This behavior could be extrapolated to other phosphorescent dinuclear three-coordinate Au(I) complexes.

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me2NCH2)C6H4]2Sb Fragment

“…50 %) (Scheme 1). This behavior is in contrast to the previous reports that described the potential of some (R 2 Sb) 2 E chalcogenides to act as terminal [15] or bridging [15][16][17][18] ligands in transition-metal complexes. The compounds were obtained as air-stable, colorless (3, 4), yellow (5), or orange (6) crystalline solids that melt without decomposition.…”

Confined Metallophilicity within a Coordination Prism

“…As shown in Figure 4, the linear geometry of two-coordinate Cu I is destructed and the CuÀN distances are significantly elongated by % 0.2 . Such an unusual phenomenon is referred to as photoinduced Jahn-Teller distortion, [10,[20][21][22] which describes the drastic geometrical adjustment in the T 1 states of d blocks and the corresponding spectroscopic uniqueness, such as huge Stokes shifts and phosphorescent emissions.…”

Synthesis and Characterization of a Gold Complex Containing [SbPh]2– and [SbPh2]– Anions as Bridging Ligands

“…Here we report the synthesis of the 12- [ [15][16][17] If one considers the estimated van der Waals radii of gold (3.6 Å), aurophilic interactions could be expected in compound 1 with Au-Au distances of 3.0100 (10) 6 ]-Br 2 [dppe, dpppe = 1,2-bis(diphenylphosphanyl)ethane or -pentane]. [11,13] Aurophilic interactions discussed in the literature for mononuclear gold complexes with Au-Au distances of about 3.05 Å are indicated in 1 by dashed-open bonds (Figure 1).…”

“…[6][7][8][9][10][11][12] However, gold complexes containing heavier group 15 elements are scarce. Recently, Au-As cluster complexes [13,14] were obtained by the synthesis of silylated arsines with Au I phosphane complexes and a few Au I complexes with tertiary ligands of the type ER 3 (E = Sb, Bi; R = organic group) are known for antimony, [15][16][17] but none for bismuth. [18] Only recently, the first Au I 2 ] with a M···Bi interaction (M = Cu, Bi) were reported.…”