Rogovoy Maxim I, Berezin Alexey S, Samsonenko Denis G, Artem'ev Alexander V
Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the RAS, 3 Academician Lavrentyev Ave., Novosibirsk 630090, Russian Federation.
Inorg Chem. 2021 May 3;60(9):6680-6687. doi: 10.1021/acs.inorgchem.1c00480. Epub 2021 Apr 19.
A series of isoreticular Ag(I) luminescent metal-organic frameworks (LMOFs), {AgL(CHCN)} (X = ClO, OTf, and BF), has been designed, exploiting diphenyl(2-pyrazyl)phosphine (L) as a multidentate linker. At ambient temperature, these compounds emit a bright long-lived phosphorescence (λ = 545-555 nm) with a quantum efficiency as high as 22%, which is the highest value for phosphorescent Ag-LMOFs. The prepared LMOFs also exhibit pronounced thermochromic luminescence, reversibly changing their emission color in the 300-77 K range. These LMOFs also demonstrate prominent solvato- and vapochromic luminescence, which manifest as a reversible change in the emission properties during the removal and recovery of the coordinated and guest MeCN molecules, respectively. Moreover, we have discovered a reversible solvent-driven 3D-to-0D transformation of the framework {AgL(CHCN)} into a brightly emissive complex [AgL(ClO)]. To the best of our knowledge, the compounds obtained are the first Ag-LMOFs that exhibit thermo-, solvato-, and vapochromic luminescence.
利用二苯基（2-吡唑基）膦（L）作为多齿连接体，设计了一系列等网状的Ag（I）发光金属有机框架（LMOF），即{AgL(CHCN)}（X = ClO、OTf和BF）。在室温下，这些化合物发出明亮的长寿命磷光（λ = 545 - 555 nm），量子效率高达22%，这是磷光Ag-LMOF的最高值。制备的LMOF还表现出明显的热致变色发光，在300 - 77 K范围内可逆地改变其发射颜色。这些LMOF还表现出显著的溶剂致变色和蒸汽致变色发光现象，分别表现为在配位的和客体MeCN分子去除和恢复过程中发射性质的可逆变化。此外，我们还发现了框架{AgL(CHCN)}向明亮发光配合物[AgL(ClO)]的可逆溶剂驱动的3D到0D转变。据我们所知，所得到的化合物是首批表现出热致变色、溶剂致变色和蒸汽致变色发光的Ag-LMOF。
