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. 2019 Oct 21;58(43):15396-15400.
doi: 10.1002/anie.201906247. Epub 2019 Sep 12.

On-Surface Reactive Planarization of Pt(II) Complexes

Jindong Ren  1   2 , Marvin Cnudde  3   2 , Dana Brünink  4 , Stefan Buss  3   2 , Constantin G Daniliuc  5 , Lacheng Liu  1   2 , Harald Fuchs  1   2 , Cristian A Strassert  3   2 , Hong-Ying Gao  1   2   6 , Nikos L Doltsinis  4
Affiliations

On-Surface Reactive Planarization of Pt(II) Complexes

Jindong Ren et al. Angew Chem Int Ed Engl. .

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).

Keywords: Pt complexes; density functional theory calculations; scanning tunnelling microscopy; surface chemistry.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Chemical structures of complexes C1–C4 and PreBr2.
Figure 1
Figure 1
Top row: STM topographies of complex C1 on Cu(111) surface at different annealing temperatures. Middle row: Close‐ups of selected areas of the images above. Bottom row: Interpretations of the highlighted areas of the STM images in the middle row in terms of molecular models.
Figure 2
Figure 2
a,b) STM topographies of the reference complex C2 on Cu(111). c) Close‐up image of moiety highlighted in Figure 1 c‐1 after annealing C1 on Cu(111). d,e) Line profiles along different directions defined in (b) and (c). f) Close‐up image of C1 on Cu(111) before annealing with molecular structure superimposed.
Figure 3
Figure 3
Top row: Constraint‐optimized structures of a C1 analogue (without the alkyl chain, but two methyl groups in meta position to speed up the calculations) on Cu(111) along the C−N dissociation path at a C−N bond length of 1.4 Å (optimized value) (a), 2.2 Å (b), and 4.4 Å (c). Second row: Optimized structures of C2 (d), C3 (e), C4 (f) on Cu(111). Bottom row: Energy profiles for C−N scission of C1, C3, and C4 on Cu(111) (g) and of C3 on Cu(111), Ag(111), and Au(111) (h).
Figure 4
Figure 4
STM topographies of complex C3 (a,b) and C4 (c,d) on Cu(111) before (a,c) and after (b,d) annealing at 385 K.
See this image and copyright information in PMC

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