Selective coordination of coinage metals using orthogonal ligand scaffolds

Abstract

Orthogonal ligand scaffolds, consisting of soft and hard donor sites, are useful tools for the selective synthesis of heteronuclear coinage metal compounds, controlling their coordination geometry and tuning their photophysical properties.

Coinage Metal Bis(amidinate) Complexes as Building Blocks for Self‐Assembled One‐Dimensional Coordination Polymers

“…[2][3][4][5][6][7][8] Moreover, monovalent coinage metal amidinate complexes are known to form dimeric species "L 2 M 2 " (M = Cu, Ag, Au), with particularly short metal-metal distances, which are "forced by the ligand environment, and go along with metallophilic interactions. [8][9][10][11][12][13][14][15][16][17][18] Recently, we reported, that these complexes may exhibit interesting photoluminescent properties. [19][20] Furthermore, in the solid state of many goldcontaining complexes these aurophilic interactions lead to the formation of dimers, oligomers, or one-dimensional selfassembled polymers.…”

“…Linkers afford a wide variety of linking sites and different binding bond strength, directionality, and sizes. [18,22,34] They range from simple halides to large organic moieties with neutral or anionic binding sites. One of the most used donor groups for organic linkers are bridged bidentate pyridyl ligands.…”

“…Therefore, they have been and continue to be used as spectator ligands in the synthesis of a wide variety of main group, transition metal and lanthanide complexes [2–8] . Moreover, monovalent coinage metal amidinate complexes are known to form dimeric species “L 2 M 2 ” (M=Cu, Ag, Au), with particularly short metal‐metal distances, which are “forced by the ligand environment, and go along with metallophilic interactions [8–18] . Recently, we reported, that these complexes may exhibit interesting photoluminescent properties [19–20] .…”

Luminescent early-late-hetero-tetranuclear group IV – Au(i) bisamidinate complexes

“…Indeed, gold(I) complexes are well known for effective phosphorescence due to the heavy atom effect which can be further modulated by metallophilic interactions. [14][15][16][17][18][19][20] Zirconium(IV) complexes, particularly derivatives exhibiting cyclopentadienyl ligands, 21 often show distinct PL in the visible spectral range as well. 22 Herein we report on the successful application of ethinylamidinates for the synthesis of tetranuclear group IVgold(I) ELHB complexes.…”

“…Indeed, gold( i ) complexes are well known for effective phosphorescence due to the heavy atom effect which can be further modulated by metallophilic interactions. 14–20 Zirconium( iv ) complexes, particularly derivatives exhibiting cyclopentadienyl ligands, 21 often show distinct PL in the visible spectral range as well. 22…”