Doping potassium ions in silver cyanide complexes for green luminescence

Abstract

Doping potassium ions in silver cyanide complexes leads to two heterometallic silver-potassium cyanide complexes, namely, [Me4N]2[KAg3(CN)6] (1) with a typical NaCl-type framework containing distinct ligand-unsupported argentophilic interactions, and [Ag3(H2O)3][K(CN)2]3 (2) with an unprecedented 3-D (4,4,6,6)-connected framework formed by unique [Ag3(H2O)3] clusters connecting concave-convex [K(CN)2] layers. The two complexes exhibit green luminescence, and the relationships between their structures and photoluminescence, as well as the regulating effect on the luminescence by doping of potassium ions are well investigated via density functional theory analysis.

Argentophilic Interactions

“…The complex shows a green luminescence in the solid state (l ex = 267, l em = 490 nm) which has been assigned to LMCT processes by DFT calculations. [233] If coordinatively saturated metal cations are present instead of quaternary ammonium cations, the dicyanoargentate(I) anions also form separate aggregates. In the three isostructural Co III , Cr III , and Ru III compounds of the type [M(NH 3 ) 6 {Ag(CN) 2 }(H 2 O) 2 ] (M = Co, Cr, Ru), the anions are organized in centrosymmetrical triples (24 b) with a staggered conformation and with Ag-Ag distances of approximately 3.15 .…”

Argentophile Wechselwirkungen

“…Die große Annäherung der [Ag(CN) 2 ] À -Anionen in den Gittern einfacher Salze wie K[Ag(CN) 2 ] oder Ca[Ag(CN) 2 ] 2 -(H 2 O) 2 unter Bildung kurzer Ag···Ag-Kontakte wurde bereits in der ganz frühen Literatur dokumentiert. [230] Diese Arbeiten wurden später unter Einbeziehung der schweren Hauptgruppenmetalle wie des in Abschnitt 2.2 erwähnten Tl[Ag(CN) 2 ] [80,231] [233] Wenn anstelle von quartären Ammoniumkationen koordinativ gesättigte Metallkationen zugegen sind, bilden die Dicyanoargentat(I)-Anionen auch separierte Aggregate. In den drei isostrukturellen Co III -, Cr III -und Ru III -Komplexen des Typs [M(NH 3 ) 6 {Ag(CN) 2 }(H 2 O) 2 ] (M = Co, Cr, Ru) organisieren sich die Anionen zu zentrosymmetrischen Dreiergruppen (24 b) mit einer gestaffelten Konformation und Ag···Ag-Abständen von ca.…”

Three Ag(I)–cyanide coordination polymers with metal bonds tuned by N-heterocyclic ligands

“…S3). Upon excitation at 391 nm, complex 1 exhibits a strong blue luminescent band with an emission peak at 457 nm, which can be assigned as metal-to-ligand charge transfer (MLCT) mechanism [12,23]. …”