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.T he 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 am odel 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-richl ocations 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.Scheme 1. Illustration of iodine-induced structuraltransformation and stabilization of elementary metal-organic motifs. Inset:chemical structure of the 9-ethylguanine molecule.

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

“…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. 47 Thus, we tentatively assign the G 3 Ni 3 Br 4 motif (Figure 1c) to a structure 4d).…”

“…In this study, we report on 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, 47 we chose a derivative of the guanine molecule (9-ethylguanine, abbreviated as G) and a NiBr 2 salt with the aim of the fabricating a three-metal-center (i.e., Ni trimer, shortened as Ni 3 ) metal-organic system on the Au( 111…”

On‐Surface Synthesis of Adenine Oligomers via Ullmann Reaction

“…Among others, scanning tunneling microscope (STM) has been widely employed due to its capability of real‐space imaging as well as manipulating at the atomic scale . Previously, self‐assembly of DNA bases and derivatives have been widely studied on different surfaces where non‐covalent interactions are mostly considered . Meanwhile, DNA macromolecules have also been introduced onto surfaces by using pulse‐injection deposition method to alleviate the difficulties in vacuum sublimation method .…”

“…[4,[7][8][9][10] Previously,s elf-assembly of DNA bases and derivatives have been widely studied on different surfaces where non-covalent interactions are mostly considered. [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] Meanwhile, DNA macromolecules have also been introduced onto surfaces by using pulse-injection deposition methodt oa lleviate the difficulties in vacuum sublimation method. [4, 8-10, 28, 29] Althougha dvanced deposition strategies have been successfully employed, it is nevertheless of general interest to explore comparatively simple routes toward in situ synthesis of DNA macromolecules on surfaces.…”

One-step hydrothermal synthesis and thermochromic properties of chlorine-doped VO2(M) for smart window application

“…The other halogen elements can be feasible to use as doping. 40 Halogen doping has been used on various materials such as graphite carbon nitride for photocatalysis, 41 HC(NH 2 ) 2 PbI 3 perovskites for solar cell, 42 thermoelectric AgBiSe 2 , 43,44 Ni catalyst, 45 stabilizing metal-organic motifs 46 and nanocarbon catalyst for oxygen reduction reaction. 43 A theoretical study of halogen doping for materials such as WS 2 have been discussed.…”