CN-121991081-A - Oxygen bridging method for regulating aromaticity and surface reaction activity of nickel (II) norcarbole derivative, and product and application thereof

CN121991081ACN 121991081 ACN121991081 ACN 121991081ACN-121991081-A

Abstract

The invention discloses a method for regulating and controlling aromaticity and surface reactivity of nickel (II) norcarbole derivatives through oxygen bridging skeleton editing, and a product and application thereof, and belongs to the technical field of surface molecular science and molecular nano-technology. In the solution phase pre-synthesis stage, a predetermined number of oxygen atoms are introduced into pyrrole-pyrrole connecting bonds of nickel (II) norcarbole molecules, and a predetermined number of C-O-C bridging structures are constructed and formed, so that precursor molecules with programmable structures are obtained. The precursor is deposited on the surface of the metal monocrystal and subjected to thermal annealing treatment to generate surface auxiliary dehydrocyclization reaction, and oxygen atoms are reserved and integrated into a final macrocyclic skeleton. The introduction of the oxygen bridge systematically regulates the electronic structure and aromatic distribution of the product, and further reconstructs the spatial distribution of the front line orbit. In the surface covalent coupling reaction, the undoped oxygen product is subjected to multi-path coupling to form products with different structures, and the oxygen bridge co-product selectively forms a single beta-beta site coupling structure.

Inventors

OuYang Zhenghao
LI KAI
HE YOUJIE
ZHANG HAONAN
HE YUANYUAN

Assignees

嘉兴大学

Dates

Publication Date: 20260508
Application Date: 20260309

Claims (10)

1. An oxygen bridging method for regulating aromaticity and surface reactivity of a nickel (II) norcarbozole derivative is characterized by comprising the following steps: (1) Synthesizing nickel (II) norcarbole derivatives in a solution phase, and inserting oxygen atoms at 0,1 or 2 pyrrole-pyrrole direct connection bonds to form a C-O-C bridging structure by the connection bonds, so as to obtain precursor molecules with different oxygen bridge numbers; (2) Depositing the precursor molecules on the surface of metal, and performing thermal annealing treatment under the condition of vacuum or inert atmosphere to enable the precursor molecules to perform surface auxiliary dehydrocyclization reaction to obtain a cyclized macrocyclic product; Wherein the oxygen atoms inserted in step (1) are retained and incorporated into the molecular skeleton of the cyclized macrocyclic product during the thermal annealing process.
2. The method of claim 1, wherein the precursor comprises: Nickel (II) norcarbole derivatives free of oxygen intercalation, hereinafter referred to as Ni (II) -Nor; Nickel (II) norcarbole derivatives, hereinafter Ni (II) -OxNor, having an oxygen atom inserted at one pyrrole-pyrrole linkage; nickel (II) norcarbole derivatives, hereinafter referred to as Ni (II) -2OxNor, having one oxygen atom inserted at each of two different pyrrole-pyrrole linkages; the introduction of the oxygen atoms is completed before the molecules are deposited onto the metal surface.
3. The method according to claim 1 or 2, characterized in that the metal surface is a Au, ag or Cu single crystal surface.
4. The method of claim 1, wherein the thermal annealing temperature is 350K-650K.
5. The method according to claim 1, wherein the cyclized macrocyclic product is a planar nickel (II) norcarbole derivative, the periphery of which forms an additional benzene ring structure by dehydrocyclization.
6. The method according to claim 1, wherein the second step is specifically: the annealing temperature is enough to trigger surface-assisted cyclodehydration reaction, so that the peripheral substituent groups of the precursor molecules and the core macrocycle are closed, and a completely-planarized and extended pi-conjugated cyclized macrocycle structure is formed; The editing effect is effective, in the process, the pre-implanted oxygen atoms in the precursor are reserved and integrated into the skeleton of the final product to form a stable C-O-C bridging structure, and the number (0, 1, 2) of the oxygen atoms is directly used as a programmable variable to determine the final electronic structure and chemical property of the cyclized product.
7. The method of claim 2, wherein the cyclized products of different numbers of oxygen bridges form dimers of different structures under the same annealing conditions, wherein: Ni (II) -nors form dimers of various structures; Ni (II) -OxNor mainly forms dimers linked to the beta-beta site.
8. A cyclized macrocyclic product prepared by the process of any one of claims 1-7, characterized in that: the product is a planar nickel (II) norcarbole derivative containing 0,1 or 2C-O-C bridges.
9. The product of claim 8, wherein the C-O-C bridge alters the aromaticity characteristics of the cyclized macrocyclic product.
10. Use of the product of claim 8 for the construction of dimers or higher order covalent assembled structures on metal surfaces by covalent coupling reactions.

Description

Oxygen bridging method for regulating aromaticity and surface reaction activity of nickel (II) norcarbole derivative, and product and application thereof Technical Field The invention belongs to the fields of surface molecular science, molecular nano technology and physical chemistry, and in particular relates to a method for performing skeleton editing on a nickel (II) norcarbole derivative on a solid surface so as to regulate and control global aromaticity and edge site reactivity. The invention also relates to the cyclized macrocyclic molecules with oxygen bridged structures prepared by this method, and their use in surface covalent assembly. Background Aromaticity and anti-aromaticity are fundamental factors affecting the electronic structure and chemical stability of pi conjugated systems, and the regulation of which is an important basis for the design of functional organic molecules and related materials. In the research direction of molecular electronics, quantum information, catalysis and the like, a great deal of work is being carried out around aromatic regulation and control. However, achieving effective modulation of molecular aromaticity and its reactive behavior in a heterogeneous and limited interfacial environment of a solid surface remains a challenge. Traditional solution phase regulation and control modes, such as oxidation reduction, protonation or ligand exchange, generally depend on solvent environment and molecular diffusion process, and are difficult to be directly applied to a surface limited domain system. In recent years, surface science has made remarkable progress in molecular adsorption, structural characterization, and surface-assisted reactions. The high-resolution scanning probe technology can analyze molecular configuration and electronic state change at a single molecular scale, and the surface auxiliary reaction is also widely used for constructing an extended pi conjugated structure and researching the electronic property of the extended pi conjugated structure. In the metal organic macrocyclic system such as porphyrin, the research of realizing pi system expansion and electronic structure adjustment through surface auxiliary reaction has been reported. These efforts have deepened the understanding of the evolution laws of the surface molecular electronic structure, but most work is based on developing surface reactions or physical field regulation of existing molecular frameworks. In contrast, by structurally designing and editing the precursor skeleton before depositing the molecules on the surface, the molecules have preset electronic structural characteristics when entering the surface reaction stage, and the researches on further influencing the surface covalent reaction behavior are relatively less. In particular, a technical scheme for influencing a subsequent surface reaction path by introducing a bridging structure into a molecular framework to change the characteristics of a pi system has not yet formed a system method. For metal organic macrocyclic molecules such as nickel (II) norcarbole, the pi electron structural characteristics of the metal organic macrocyclic molecules endow the metal organic macrocyclic molecules with specific aromatic or anti-aromatic behaviors, and various competing paths can be presented in the surface reaction process. How to control the aromatic character of the molecules and further influence the reaction selectivity of the covalent coupling of the surface by structurally modulating the core backbone before the molecules are deposited on the surface remains to be solved. Disclosure of Invention The invention provides a technical scheme for influencing the aromatic character and the surface reaction behavior of a molecular precursor skeleton by carrying out structural adjustment under the surface synthesis condition. The existing surface chemical method is mainly based on the established molecular structure to carry out surface reaction or physical field regulation and control, and lacks technical means for regulating the subsequent surface reaction path through the framework structure design before the molecules are deposited on the surface. The core of the invention is to provide a regulation strategy based on oxygen bridging skeleton editing. In the strategy, 0, 1 or 2 oxygen atoms are introduced into pyrrole-pyrrole connecting bonds of the nickel (II) norcarbole derivative in the solution phase pre-synthesis stage to form a certain number of C-O-C bridging structures. The oxygen bridge structure is retained and integrated into the final product backbone during subsequent surface thermal activation, thereby imparting different aromaticity characteristics and surface reaction behavior to the resulting cyclized product. The core method of the invention is based on precursor design and surface heat activated skeleton editing The method comprises the following steps: 1. Designing and synthesizing precursor molecules of oxygen-contai