Review: Multimetallic silver(I)–pyridinyl complexes: coordination of silver(I) and luminescence

Silver(I) Clusters with Carba‐closo‐dodecaboranylethynyl Ligands: Synthesis, Structure, and Phosphorescence

“…[6] One appealing feature of silver(I)-alkynyl complexes is their multifarious coordination chemistry. [7] Mosts ilver(I)c luster syntheses start from the neat alkynyl species, whichi st ypically ab arely soluble coordination polymer, [9] and ac o-ligand such as pyridine [10] or at emplate reagent. [7] Mosts ilver(I)c luster syntheses start from the neat alkynyl species, whichi st ypically ab arely soluble coordination polymer, [9] and ac o-ligand such as pyridine [10] or at emplate reagent.…”

“…In addition, the crystal structures of [Ag 16 (12-CCcloso-1-CB 11 H 11 ) 8 (Py) 9.25 (CH 3 CN) 2 (CH 2 Cl 2 ) 0.75 ]·CH 2 Cl 2 , [Ag 8 (12-CC-closo-1-CB 11 H 11 ) 4 (Py) 12 ], [Ag 10 (12-CC-closo-1-CB 11 H 11 ) 4 (4-MePy) 10 Br 2 ], [Ag 7 (12-CC-closo-1-CB 11 H 11 ) 3 (4-tBu-Py) 11 Cl]·(4-tBuPy), and [Ag 9 (12-CC-closo-1-CB 11 H 11 ) 4 (3,5-Me 2 Py) 11 Cl] were elucidated. In contrast, 3,5-lutidine (3,5-Me 2 Py) did not result in salts of dianionic clusters, even in the presence of excess of [Et 4 N]Cl or [Ph 4 P]Br;i nstead salts of monoanionic Ag I 7 clusters, [Et 4 N][Ag 7 (12-CC-closo-1-CB 11 H 11 ) 4 (3,5-Me 2 Py) 9 ]and [Ph 4 P][Ag 7 (12-CC-closo-1-CB 11 H 11 ) 4 (3,5-Me 2 Py) 13 ]w ere obtained.T he Ag I 7 clusteri sp entagonal bipyramidal in the former,b ut is an edge-capped octahedron in the latter.T he 4-methylpyridine and 3,5-lutidine complexes show green phosphorescence at room temperature.…”

Unprecedented Efficient Structure Controlled Phosphorescence of Silver(I) Clusters Stabilized by Carba‐closo‐dodecaboranylethynyl Ligands

“…[1e,f] In contrast to silver(I) alkynyl compounds, which are often hardly soluble and structurally difficult-tocharacterize coordination polymers, [4] well-defined Ag I clusters with donor ligands (e.g. pyridine [5] ), as silver(I) double salts, [1e,f] or with templates [1g, 6] are more easily accessible.Selforganization to yield coordination polymers or clusters is mainly due to 1) the flexible coordination of Ag I ions to more than one alkynyl ligand, 2) bridging alkynyl ligands,a nd 3) argentophilic interactions. [2,7] Argentophilic interactions are structure-determining dispersive interactions between metal ions with ad 10 valence electron configuration, [8] with aurophilicity as prototype.…”

“…[14b] Thecoordination of Ag I ions to Hatoms of {closo-1-CB 11 }cages was observed, previously. Single crystals of the silver(I) complexes were obtained from pyridine (2)o racetone (3)(4)(5). Single crystals of the silver(I) complexes were obtained from pyridine (2)o racetone (3)(4)(5).…”

The Nature of Metal–Metal Interactions in Dimeric Hydrides and Halides of Group 11 Elements in the Light of High Level Relativistic Calculations

“…[5] Another criterion used as an evidence of such attractions is the presence of a( 3,-1) critical point [6] (CP,b ond critical point, BCP,f or the equilibrium structure [6] )between two Matoms [7] in amolecular graph of am olecule (crystal). [9] Luminescencee xhibited by Cu I , [10] Ag I , [1,3,11] and Au I[2, 12] complexes is often believed to be indicative of metallophilic interactions.Also, an experimental (see, for example, Ta ble 5i nR ef. Indeed,t he presence of aB CP is not always associated with attractive interactions.…”