On‐Surface Reactive Planarization of Pt(II) Complexes
On‐Surface Reactive Planarization of Pt(II) Complexes
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DOI：
10.1002/anie.201906247
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发表时间：
2019-07
期刊：
影响因子：
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通讯作者：
Jindong Ren;Marvin Cnudde;Dana Brünink;Stefan Buss;C. Daniliuc;Lacheng Liu;H. Fuchs;C. Strassert;Hongying Gao;N. Doltsinis
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文献类型：
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作者：
Jindong Ren;Marvin Cnudde;Dana Brünink;Stefan Buss;C. Daniliuc;Lacheng Liu;H. Fuchs;C. Strassert;Hongying Gao;N. Doltsinis
摘要设计、合成了一系列具有四齿发光团的Pt（II）配合物，并将其沉积在硬币金属表面上，目的是制备高度平面的自组装单层。低温扫描隧道显微镜（STM）和密度泛函理论（DFT）计算揭示了所有配合物的初始非平面性。在随后的金属催化下，通过C - N键的断裂，桥接单元上的非平面部分分离，留下了一个很大的平面核心配合物。发现该键断裂过程的激活势垒强烈依赖于桥接基和配位面的化学性质，并从Cu（111）→Ag（111）→Au（111）增加。
Abstract A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces with the aim to produce highly planar self‐assembled monolayers. Low‐temperature scanning tunneling microscopy (STM) and density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. A subsequent metal‐catalyzed separation of the nonplanar moiety at the bridging unit via the scission of a C−N bond is observed, leaving behind a largely planar core complex. The activation barrier of this bond scission process is found to depend strongly on the chemical nature of both bridging group and coordination plane, and to increase from Cu(111) through Ag(111) to Au(111).