Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

Abstract

The structural transformation of supramolecular nanostructures with constitutional diversity and adaptability by dynamic coordination chemistry would be of fundamental importance for potential applications in molecular switching devices. The role of halogen doping in the formation of elementary metal-organic motifs on surfaces has not been reported. Now, the 9-ethylguanine molecule (G) and Ni atom, as a model system, are used for the structural transformation and stabilization of metal-organic motifs induced by iodine doping on Au(111). The iodine atoms are homogeneously located at particular hydrogen-rich locations enclosed by G molecules by electrostatic interactions, which would be the key for such an unexpected stabilizing effect. The generality and robustness of this approach are demonstrated in different metal-organic systems (G/Fe) and also by chlorine and bromine.

Switching the Spin on a Ni Trimer within a Metal–Organic Motif by Controlling the On-Top Bromine Atom

“…In this study, we report the manipulation of the magnetic state of a multiple-metal center in a molecular assembly by addition/removal of Br atoms. Based on our previous study, we chose a derivative of the guanine molecule (9-ethylguanine, abbreviated as G) and a NiBr 2 salt with the aim of fabricating a three-metal-center ( i.e. , Ni trimer, shortened as Ni 3 ) metal–organic system on the Au(111) surface.…”

“…This assignment is also confirmed by the Br removal experiment discussed below. The structural motif beneath the central Br atom coincides in size and shape with the structure of the basic motif of G 3 Ni 3 I 3 assemblies reported previously . Thus, we tentatively assign the G 3 Ni 3 Br 4 motif (Figure c) to a structure formed by a G 3 Ni 3 Br 3 base with an additional Br atom sitting on the hollow site of the central Ni 3 cluster.…”

Atomic‐Scale Visualization of the Stepwise Metal‐Mediated Dehalogenative Cycloaddition Reaction Pathways: Competition between Radicals and Organometallic Intermediates

“…Additionally, the adsorption directions of the molecules are 15±2° off from the original ones. The dots are located close to hydrogen‐rich harbors, and such a behavior is regarded as characteristic of halogen atoms owing to electrostatic interactions . It is noteworthy that even at about 220 K, very few debr‐HBTP and locally dissociated Br atoms exist in the initial islands (Supporting Information, Figure S3).…”

Construction and manipulation of self-assemble structures on solid surfaces

“…[76] . 图 10 G分子、镍原子、碘原子形成的金属-有机分子网格结构 [78] . (a~c) G 3 Ni 1 、G 2 Ni 2 和G 3 Ni 3 三种不同的结构, (e~g) 相应的 原子结构图.…”

“…(a~c) G 3 Ni 1 、G 2 Ni 2 和G 3 Ni 3 三种不同的结构, (e~g) 相应的 原子结构图. (d) 沉积碘以后形成的G 3 Ni 3 I 3 蜂窝状网格结构, (h) 相应的高分辨率图像和原子结构图(网络版彩图) Figure 10 Self-assembled structures constructed by G molecules, nickel atoms and iodine atoms [78]. (a-c) Large-scale STM images showing different structures of G 3 Ni 1 , G 2 Ni 2 and G 3 Ni 3 .…”