"Quick-Silver" from a Systematic Study of Highly Luminescent, Two-Coordinate, d10 Coinage Metal Complexes
"Quick-Silver" from a Systematic Study of Highly Luminescent, Two-Coordinate, d10 Coinage Metal Complexes
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DOI：
10.1021/jacs.9b03657
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发表时间：
2019-05-29
影响因子：
15
通讯作者：
Thompson, Mark E.
中科院分区：
文献类型：
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作者：
Hamze, Rasha;Shi, Shuyang;Thompson, Mark E.
对具有共同酰胺（N-咔唑基）和两种不同卡宾配体（即 CAAC = (5R,6S)-2-(2,6-二异丙基-苯基1)-6-异丙基1-3,3,9-三甲基-2-氮杂螺[4.5]的等电子和同结构铜、银和金配合物的物理和光物理性质进行了系统研究癸-2-亚基，MAC = 1,3-双(2,6-二异丙基苯基1)-5,5-二甲基1-4-酮-四氢吡啶基)。 (卡宾)M-(I)(N-咔唑基1) (M-CAAC)和(MAC)M-(I)(N-咔唑基1) (M-MAC)配合物的晶体结构显示出共面的卡宾和咔唑配体以及类似于180度的C-M-N键角。金属离子的选择不会显着影响电荷转移（CT）吸收和发射化合物的电化学性质和能量。这里检查的所有六种 (卡宾)M(Cz) 配合物均显示出 0.8-1.0 的高光致发光量子产率。这些化合物的发射寿命很短（tau = 0.33-2.8 μs），其顺序为 Ag < Au < Cu，其中 (卡宾)Ag(Cz) 的寿命大约比 (卡宾)Cu(Cz) 配合物的寿命短 10 倍。进行了详细的温度依赖性光物理测量（5-325 K），以确定单重态和三重态发射寿命（分别为 tau（fl）和 tau（ph））以及单重态和三重态激发态之间的能量差 Delta（Si-Ti）。 tau(fl) 值范围在 20 到 85 ns 之间，tau(ph) 值在 50-200 mu s 范围内。室温下的发射完全归因于 E 型延迟荧光或 TADF（即 T-1 Delta -> S-1 > S-0 + h upsilon）。室温下的发射速率完全由 Delta(Si)-(Ti) 控制，银络合物给出 AEsi_T，值为 150-180 cm-1 (18-23 meV)，而金和铜络合物给出值为 570-590 cm(-1) (70-73 meV)。
A systematic study is presented on the physical and photophysical properties of isoelectronic and isostructural Cu, Ag, and Au complexes with a common amide (N-carbazolyl) and two different carbene ligands (i.e., CAAC = (5R,6S)-2-(2,6-diisopropyl-pheny1)-6-isopropy1-3,3,9-trimethyl-2-azaspiro [4.5] decan-2-ylidene, MAC = 1,3-bis(2,6-diisopropylpheny1)-5,5-dimethy1-4-keto-tetrahydropyridylidene). The crystal structures of the (carbene)M-(I)(N-carbazoly1) (M-CAAC) and (MAC)M-(I)(N-carbazoly1) (M-MAC) complexes show coplanar carbene and carbzole ligands and C-M-N bond angles of similar to 180 degrees. The electrochemical properties and energies for charge transfer (CT) absorption and emission compounds are not significantly affected by the choice of metal ion. All six of the (carbene)M(Cz) complexes examined here display high photoluminescence quantum yields of 0.8-1.0. The compounds have short emission lifetimes (tau = 0.33-2.8 mu s) that fall in the order Ag < Au < Cu, with the lifetimes of (carbene)Ag(Cz) roughly a factor of 10 shorter than for (carbene)Cu(Cz) complexes. Detailed temperature-dependent photophysical measurements (5-325 K) were carried out to determine the singlet and triplet emission lifetimes (tau(fl) and tau(ph), respectively) and the energy difference between the singlet and triplet excited state, Delta(Si-Ti). The tau(fl) values range between 20 and 85 ns, and the tau(ph) values are in the 50-200 mu s regime. The emission at room temperature is due exclusively to E-type delayed fluorescence or TADF (i.e., T-1 Delta -> S-1 > S-0 + h upsilon). The emission rate at room temperature is fully governed by Delta(Si)-(Ti), with the silver complexes giving AEsi_T, values of 150-180 cm-1 (18-23 meV), whereas the gold and copper complexes give values of 570-590 cm(-1) (70-73 meV).