TY - JOUR
T1 - Synthesis and Comparison of the Photophysical Properties of Anionic Diaryl [M(C^C)(CN)2]x− (M= AuIII, PtII) Complexes
AU - Gomez de Segura, Iker Gil
AU - Martin, Antonio
AU - Bochmann, Manfred
AU - Lalinde, Elena
AU - Fernandez-Cestau, Julio
PY - 2026/5/10
Y1 - 2026/5/10
N2 - The d
8 complexes A[Au(C^C)(CN)
2] and A
2[Pt(ĈC)(CN)
2] (where C^C = 4,4′-di-tert-butylbiphenyl-2,2′-diyl and A
+ = NBu
4
+, K
+) were synthesized from [Au(C^C)Cl]
2 and [Pt(C^C)COD], which were themselves obtained from Sn(C^C)
nBu
2. These complexes are bright photoemitters but exhibit remarkable differences in the origin of their photoluminescence. The tin complex Sn(C^C)
nBu
2 displays blue/white photoluminescence originating from an admixture of transitions. In contrast, the gold complexes exhibit green, long-lived phosphorescence (lifetimes up to 100 μs), which theoretical calculations attribute to
3IL(C^C) transitions. Although the platinum complexes show similar absorption and emission energies, theoretical calculations indicate an admixture with
3MLCT character in their emissive states. This is evidenced by (i) luminescence lifetimes up to 1 order of magnitude shorter than those of the gold complexes under similar conditions; (ii) a greater contribution from fluorescence with respect to phosphorescence in solution, and (iii) reduced susceptibility to
3O
2 quenching, a consequence of the shorter triplet-state lifetime. The combination of water solubility, efficient ISC, and a long-lived triplet state with high sensitivity to dissolved O
2 endows K[Au(C^C)(CN)
2] with excellent catalytic activity in the photo-oxidation of p-bromothioanisole. This result underscores the potential of this class of Au(III) salts for photocatalysis in green solvents.
AB - The d
8 complexes A[Au(C^C)(CN)
2] and A
2[Pt(ĈC)(CN)
2] (where C^C = 4,4′-di-tert-butylbiphenyl-2,2′-diyl and A
+ = NBu
4
+, K
+) were synthesized from [Au(C^C)Cl]
2 and [Pt(C^C)COD], which were themselves obtained from Sn(C^C)
nBu
2. These complexes are bright photoemitters but exhibit remarkable differences in the origin of their photoluminescence. The tin complex Sn(C^C)
nBu
2 displays blue/white photoluminescence originating from an admixture of transitions. In contrast, the gold complexes exhibit green, long-lived phosphorescence (lifetimes up to 100 μs), which theoretical calculations attribute to
3IL(C^C) transitions. Although the platinum complexes show similar absorption and emission energies, theoretical calculations indicate an admixture with
3MLCT character in their emissive states. This is evidenced by (i) luminescence lifetimes up to 1 order of magnitude shorter than those of the gold complexes under similar conditions; (ii) a greater contribution from fluorescence with respect to phosphorescence in solution, and (iii) reduced susceptibility to
3O
2 quenching, a consequence of the shorter triplet-state lifetime. The combination of water solubility, efficient ISC, and a long-lived triplet state with high sensitivity to dissolved O
2 endows K[Au(C^C)(CN)
2] with excellent catalytic activity in the photo-oxidation of p-bromothioanisole. This result underscores the potential of this class of Au(III) salts for photocatalysis in green solvents.
UR - https://www.scopus.com/pages/publications/105039979435
U2 - 10.1021/acs.inorgchem.6c00495
DO - 10.1021/acs.inorgchem.6c00495
M3 - Article
SN - 0020-1669
VL - 65
SP - 11024
EP - 11035
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 20
ER -