Hailmann Michael, Wolf Natalia, Renner Rebecca, Hupp Benjamin, Steffen Andreas, Finze Maik
Institut für Anorganische Chemie, Institut für nachhaltige Chemie und Katalyse mit Bor (ICB), Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2017 Aug 25;23(48):11684-11693. doi: 10.1002/chem.201702515. Epub 2017 Aug 3.
Salts of anionic silver(I) clusters with the carba-closo-dodecaboranylethynyl ligand were obtained from {Ag (12-C≡C-closo-1-CB H )} , selected pyridines, and [Et N]Cl or [Ph P]Br. Salts of octahedral silver(I) clusters [Et N] [Ag (12-C≡C-closo-1-CB H ) (4-X-C H N) ] were formed with pyridine (X=H, x=8), 4-methylpyridine (X=Me, x=8), and 4-cyanopyridine (X=CN, x=10). In contrast, 3,5-lutidine (3,5-Me Py) did not result in salts of dianionic clusters, even in the presence of excess of [Et N]Cl or [Ph P]Br; instead salts of monoanionic Ag clusters, [Et N][Ag (12-C≡C-closo-1-CB H ) (3,5-Me Py) ] and [Ph P][Ag (12-C≡C-closo-1-CB H ) (3,5-Me Py) ] were obtained. The Ag cluster is pentagonal bipyramidal in the former, but is an edge-capped octahedron in the latter. The 4-methylpyridine and 3,5-lutidine complexes show green phosphorescence at room temperature. Although argentophilic interactions give rise to sufficient spin-orbit coupling for intersystem crossing S →T and moderate-to-high radiative rate constants, time-resolved measurements indicate that the quantum yields are greatly influenced by the pyridine ligands, which mainly determine the non-radiative rate constants. In addition, the crystal structures of [Ag (12-C≡C-closo-1-CB H ) (Py) (CH CN) (CH Cl ) ]⋅CH Cl , [Ag (12-C≡C-closo-1-CB H ) (Py) ], [Ag (12-C≡C-closo-1-CB H ) (4-MePy) Br ], [Ag (12-C≡C-closo-1-CB H ) (4-tBuPy) Cl]⋅(4-tBuPy), and [Ag (12-C≡C-closo-1-CB H ) (3,5-Me Py) Cl] were elucidated.
阴离子银（I）簇与碳硼烷乙炔基配体形成的盐是由{Ag(12-C≡C-closo-1-CB₁₁H₁₁)}、选定的吡啶以及[Et₄N]Cl或[Ph₃P]Br制得的。八面体银（I）簇盐[Et₄N][Ag(12-C≡C-closo-1-CB₁₁H₁₁)(4-X-C₅H₄N)₂]是由吡啶（X = H，x = 8）、4-甲基吡啶（X = Me，x = 8）和4-氰基吡啶（X = CN，x = 10）形成的。相比之下，3,5-二甲基吡啶（3,5-Me₂Py）即使在过量[Et₄N]Cl或[Ph₃P]Br存在的情况下也不会生成双阴离子簇盐；相反，得到了单阴离子银簇盐[Et₄N][Ag(12-C≡C-closo-1-CB₁₁H₁₁)(3,5-Me₂Py)]和[Ph₃P][Ag(12-C≡C-closo-1-CB₁₁H₁₁)(3,5-Me₂Py)]。在前一种盐中银簇为五角双锥结构，而在后一种盐中为边帽八面体结构。4-甲基吡啶和3,5-二甲基吡啶配合物在室温下呈现绿色磷光。尽管亲银相互作用产生了足够的自旋-轨道耦合用于系间窜越S→T以及中等至高的辐射速率常数，但时间分辨测量表明量子产率受吡啶配体的极大影响，吡啶配体主要决定了非辐射速率常数。此外，还阐明了[Ag(12-C≡C-closo-1-CB₁₁H₁₁)(Py)(CH₃CN)(CH₂Cl₂)]⋅CH₂Cl₂、[Ag(12-C≡C-closo-1-CB₁₁H₁₁)(Py)₂]、[Ag(12-C≡C-closo-1-CB₁₁H₁₁)(4-MePy)Br]、[Ag(12-C≡C-closo-1-CB₁₁H₁₁)(4-tBuPy)Cl]⋅(4-tBuPy)和[Ag(12-C≡C-closo-1-CB₁₁H₁₁)(3,5-Me₂Py)Cl]的晶体结构。
