Selenium-Centered, Undecanuclear Silver Cages Surrounded by Iodo and Dialkyldiselenophosphato Ligands. Syntheses, Structures, and Photophysical Properties

Abstract

Three clusters [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}6] (R = Et, 1; iPr, 2; 2Bu, 3) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se2P(OR)2], and Bu4NI in a molar ratio of 4:3:1 in CH2Cl2 in 47-55% yield. Compounds 1 and 2 can also be synthesized with high yield from the reaction of Ag10(Se)[Se2P(OR)2]8 with 8 equiv of Bu4NI. In the positive fast atom bombardment mass spectra of 1-3, two major peaks that correspond to the intact molecule with the loss of an iodide ion, [Ag11(mu9-Se)(mu3-I)(2){Se2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}5]+, were identified. Single-crystal X-ray analyses of 2 and 3 reveal an Ag11Se core stabilized by three iodide anions and six diselenophosphato ligands in a tetrametallic tetraconnective (mu2,mu2) coordination mode. The central core adopts the geometry of a 3,3,4,4,4-pentacapped trigonal prism with a selenium atom in the center. In addition, weak intermolecular Se...I interactions exist in 2 and form a one-dimensional polymeric chain structure. Furthermore, all compounds exhibit orange-red luminescence in both the solid state and solution.

Argentophilic Interactions

“…This mode of clustering has also been found with halide anions as coordination centers (see Section 3.4.2). [177] Thiolato instead of sulfido bridging of silver atoms is more common, and examples have been described for a variety of thiol precursors. In early work it was shown that the general formula [{RSAg} n ] applies for both ring and chain structures.…”

Metal Nanoclusters Stabilized by Selenol Ligands

“…The atomically precise structures of such small complexes enable cluster researchers to understand the initial state of Ag–Se interactions . The Liu group has made great contributions in this field . Structures of several H‐centered, Br‐centered, I‐centered, and Se‐centered silver complexes have been determined, including H@Ag 7 {Se 2 P(O i Pr) 2 } 6 , Br@Ag 8 {Se 2 P(OEt) 2 } 6 (Figure d), H@Ag 8 {Se 2 P(O i Pr) 2 } 6 (Figure e), I@Ag 11 ( µ 3 ‐I) 3 {Se 2 P(O i Pr) 2 } 6 , Se@Ag 10 {Se 2 P(OEt) 2 } 8 (Figure f), (Br/I)@Ag 12 {Se 2 P(OEt) 2 } 10 , and so on.…”

Argentophile Wechselwirkungen

“…Diese Form der Clusterbildung wurde auch mit Halogenidanionen als Koordinationszentren gefunden. [177] Thiolat-anstelle von Sulfidverbrückung von Silberatomen wird häufiger beobachtet, und es gibt Beispiele für eine große Auswahl an Thiolvorstufen. In frühen Arbeiten wurde gezeigt, dass die allgemeine Formel [{RSAg} n ] sowohl für Ringals auch für Kettenstrukturen gilt.…”