CN114292201B - Compound with quantum interference effect and single-molecule field effect transistor comprising same - Google Patents

Compound with quantum interference effect and single-molecule field effect transistor comprising same Download PDF

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CN114292201B
CN114292201B CN202111615533.7A CN202111615533A CN114292201B CN 114292201 B CN114292201 B CN 114292201B CN 202111615533 A CN202111615533 A CN 202111615533A CN 114292201 B CN114292201 B CN 114292201B
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graphene
effect transistor
field effect
compound
molecule field
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CN114292201A (en
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郭雪峰
李佩慧
贾传成
汪博宇
常新月
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Beijing Weimingyuanshang Molecular Technology Co ltd
Nankai University
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Beijing Weimingyuanshang Molecular Technology Co ltd
Nankai University
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Abstract

The application provides a compound with quantum interference effect and a single-molecule field effect transistor containing the compound, and the single-molecule field effect transistor has an order of magnitude improvement in switching ratio compared with a field effect transistor constructed by common molecules due to the quantum interference effect. In the single-molecule field effect transistor, the compound with quantum interference effect can be stably connected with the gap of the two-dimensional single-layer graphene with the nano gap array through the amide covalent bond to form a molecular heterojunction, novel two-dimensional materials with atomic level flatness and controllable atomic layer thickness are adopted, van der Waals heterostructures are formed through Van der Waals stacking assembly of different two-dimensional materials, accurate control preparation of the single-molecule field effect transistor device can be realized, the single-molecule field effect transistor has strong gate electric field regulation capability, and good stability and integration are achieved.

Description

Compound with quantum interference effect and single-molecule field effect transistor comprising same
Technical Field
The present application relates to the field of field effect transistors, and in particular, to a compound having a quantum interference effect and a single-molecule field effect transistor including the compound.
Background
The rapid growth of nanotechnology research has led to great implications for the development of computing devices, solar energy harvesting, chemical sensing, photonics and optoelectronics, biomedical electronics (e.g., cell-chip connections, electronic cells, electronic therapies and repair), and biofuel cells. The development of electronic devices based on controllable molecular conduction meets, on the one hand, the urgent need for further device miniaturization and, on the other hand, the need for organic and inorganic materials for biomedical and nanoelectronic applications. The organic molecular field effect transistor has molecular level size, and the application of gate voltage in the molecular heterojunction can regulate and control the energy level position of the molecule, so that the relative position of the molecular energy level and the fermi level of the electrode is changed, and the conductivity of the molecule is regulated and controlled.
At present, the most mature system in the regulation strategy of the single-molecule field effect transistor device is based on an electrostatic field generated by a traditional solid gate, but the regulation efficiency of the regulation method is lower, the stability and the integration of the single-molecule field effect transistor device are poor, the device is sensitive to the thickness of a dielectric layer, particularly the existing dielectric layer is mostly made of silicon dioxide, hafnium dioxide and other materials, the preparation of the solid dielectric layer with the thickness matched with the molecular size is extremely difficult in process implementation, and the application of the silicon dioxide in the prior manufacturing process is limited by the lower dielectric constant of the silicon dioxide. Therefore, it is necessary to develop a single-molecule field effect transistor with strong gate electric field regulation capability, good stability and integration.
Disclosure of Invention
The application aims to provide a compound with quantum interference effect and a single-molecule field effect transistor comprising the compound, so as to obtain the single-molecule field effect transistor with stronger gate electric field regulation and control capability, better stability and integration.
The specific technical scheme is as follows:
the first aspect of the application provides a compound with quantum interference effect, which has a structural formula shown as formula A:
H2N-R2-R1-R2-NH2
Formula A;
wherein R 1 is selected from any one of formulas I-VI;
R 2 is selected from- (CH 2)m) -or M is an integer of 1 to 6;
R, rx and Ry are each independently selected from CH 3(CH2)n, and n is an integer from 0 to 5.
The second aspect of the present application provides a single molecule field effect transistor comprising any one of the compounds having quantum interference effects provided in the first aspect of the present application.
The third aspect of the present application provides a method for manufacturing a single-molecule field effect transistor, comprising the steps of:
1) Preparing a graphene gate electrode layer on a substrate;
2) Preparing a Bi 2SeO5 dielectric layer on the upper surface of the graphene gate electrode layer;
3) Preparing a graphene electrode layer on the upper surface of the Bi 2SeO5 dielectric layer;
4) Constructing a nano gap on the graphene electrode layer to obtain a graphene point electrode, wherein the graphene point electrode comprises a graphene source end electrode and a graphene drain end electrode;
5) Connecting a graphene point electrode with a molecular heterojunction through an amide bond; the molecular heterojunction is composed of any one of the compounds with quantum interference effect provided in the first aspect of the application;
6) And covering the upper surfaces of the graphene point electrode and the molecular heterojunction with an h-BN protective layer to obtain the single-molecule field effect transistor.
The present application provides a compound having a quantum interference effect and a single-molecule field effect transistor including the same, which has an order of magnitude improvement in switching ratio compared to a field effect transistor constructed of a general molecule due to the quantum interference effect. In the single-molecule field effect transistor, the compound with quantum interference effect can be stably connected with the gap of the two-dimensional single-layer graphene with the nano gap array through the amide covalent bond to form a molecular heterojunction, novel two-dimensional materials with atomic level flatness and controllable atomic layer thickness are adopted, van der Waals heterostructures are formed through Van der Waals stacking assembly of different two-dimensional materials, accurate control preparation of the single-molecule field effect transistor device can be realized, the single-molecule field effect transistor has strong gate electric field regulation capability, and good stability and integration are achieved.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the application, and other embodiments may be obtained according to these drawings to those skilled in the art.
Fig. 1 is a perspective view of a single-molecule field effect transistor of example 1; the reference numerals are: 1. the graphene comprises a graphene gate electrode layer, a 2.Bi 2SeO5 dielectric layer, a 3.graphene source electrode, a 4.graphene drain electrode, a 5.molecular heterojunction formed by a compound A1 and a 6.h-BN protective layer.
Fig. 2 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 1 at a gate voltage of 0V.
Fig. 3 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 1 when the bias voltage is 0.1V.
Fig. 4 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 2 when the gate voltage is 0V.
Fig. 5 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 2 when the bias voltage is 0.1V.
Fig. 6 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 3 when the gate voltage is 0V.
Fig. 7 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 3 when the bias voltage is 0.1V.
Fig. 8 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 4 when the gate voltage is 0V.
Fig. 9 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 4 when the bias voltage is 0.1V.
Fig. 10 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 5 when the gate voltage is 0V.
Fig. 11 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 5 when the bias voltage is 0.1V.
Fig. 12 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 6 when the gate voltage is 0V.
Fig. 13 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 6 when the bias voltage is 0.1V.
Fig. 14 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 7 when the gate voltage is 0V.
Fig. 15 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 7 when the bias voltage is 0.1V.
Fig. 16 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 8 when the gate voltage is 0V.
Fig. 17 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 8 when the bias voltage is 0.1V.
Fig. 18 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 9 when the gate voltage is 0V.
Fig. 19 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 9 when the bias voltage is 0.1V.
Fig. 20 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 10 when the gate voltage is 0V.
Fig. 21 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 10 when the bias voltage is 0.1V.
Fig. 22 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 11 when the gate voltage is 0V.
Fig. 23 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 11 when the bias voltage is 0.1V.
Fig. 24 is a graph showing the current-bias characteristics of the single-molecule field effect transistor of example 12 when the gate voltage is 0V.
Fig. 25 is a graph showing the current versus gate voltage for the single-molecule field effect transistor of example 12 when the bias voltage is 0.1V.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. Based on the embodiments of the present application, all other embodiments obtained by the person skilled in the art based on the present application are included in the scope of protection of the present application.
The first aspect of the application provides a compound with quantum interference effect, which has a structural formula shown as formula A:
H2N-R2-R1-R2-NH2
Formula A;
wherein R 1 is selected from any one of formulas I-VI;
R 2 is selected from- (CH 2)m) -or M is an integer of 1 to 6;
R, rx and Ry are each independently selected from CH 3(CH2)n, and n is an integer from 0 to 5.
In some embodiments of the first aspect of the application, the compound having a quantum interference effect is selected from any one of formulas A1-a 12:
The second aspect of the present application provides a single molecule field effect transistor comprising any one of the compounds having quantum interference effects provided in the first aspect of the present application.
The application comprises the single-molecule field effect transistor with the quantum interference effect compound, and due to the quantum interference effect, quantum interference cancellation effect can occur when electrons are transmitted through a specific molecular orbit of a molecular functional unit in the single-molecule field effect transistor device, so that the electron transport capacity is reduced by orders of magnitude in an off state compared with that of a common molecule, and therefore, the switching ratio of the single-molecule field effect transistor is improved by orders of magnitude compared with that of a field effect transistor constructed by the common molecule. In the single-molecule field effect transistor containing the compound with the quantum interference effect, the compound with the quantum interference effect can be stably connected with gaps of two-dimensional single-layer graphene with a nano gap array through an amide covalent bond to form a molecular heterojunction, two-dimensional materials with flat atomic level and controllable atomic layer thickness are adopted, and Van der Waals stacking assembly of different two-dimensional materials is adopted to form a Van der Waals heterostructure, so that the single-molecule field effect transistor has strong gate electric field regulation capability and good stability and integration.
In some embodiments of the second aspect of the present application, the single-molecule field effect transistor further comprises a graphene gate electrode layer, a Bi 2SeO5 dielectric layer, a graphene source terminal electrode, a graphene drain terminal electrode, a molecular heterojunction, and an h-BN protective layer; the molecular heterojunction is composed of the compound with quantum interference effect.
The application adopts the two-dimensional material bismuth oxyselenite (Bi 2SeO5) as a dielectric layer, has high dielectric constant (kappa=21) and good insulating property, and can provide stronger gate electric field regulation and control capability; and hexagonal boron nitride (h-BN) is used as a protective layer for packaging, so that the interference of the external environment can be greatly reduced, and the stability of the single-molecule field effect transistor is further improved.
The two-dimensional material adopted by the application has a layered crystal structure with strong in-plane covalent bonds, and the surface has no dangling bonds, so that the two-dimensional material can also show excellent electronic and optical properties even under the limit of single-atom thickness; meanwhile, the two-dimensional material layers are coupled together through weak van der Waals force (vdW) to form a van der Waals heterostructure, so that the tight contact between the layers can be kept, and the stability of the single-molecule field effect transistor is improved; and the plane processability of the two-dimensional material is favorable for improving the integration of the single-molecule field effect transistor.
According to the single-molecule field effect transistor containing the compound with the quantum interference effect shown in the formula A, the compound with the quantum interference effect can be stably connected to gaps of two-dimensional single-layer graphene with the nano gap array through amide covalent bonds to form a molecular heterojunction, a novel two-dimensional material is adopted to replace grid and dielectric layer materials in a traditional field effect transistor, a van der Waals heterostructure is formed through van der Waals stacking assembly of different two-dimensional materials, the dielectric layer and the grid of the single-molecule field effect transistor reach the level of atoms and the thickness of an atomic layer is controllable, accurate control preparation of the single-molecule field effect transistor device is achieved, and the single-molecule field effect transistor has strong grid electric field regulation capability, good stability and integration.
In the present application, the thickness of each two-dimensional material layer is required to be matched with the molecular size of the compound having the quantum interference effect, and the specific thickness of each two-dimensional material layer is not particularly limited as long as the object of the present application can be achieved, and in some embodiments of the second aspect of the present application, the thickness of the graphene gate electrode layer may be 0.7-20nm; the thickness of the Bi 2SeO5 dielectric layer can be 1-20nm; the thickness of the h-BN protective layer may be 0.7-20nm; the thickness of the graphene source end electrode can be 0.7-3nm; the thickness of the graphene drain electrode can be 0.7-3nm; the thickness of the molecular heterojunction can be 0.7-3nm; the thicknesses of the graphene source electrode and the graphene drain electrode and the thickness of the molecular heterojunction can be the same or different. Wherein the thickness of the Bi 2SeO5 dielectric layer is 1-20nm, and the corresponding applicable grid voltage is 0.1-10V.
In some embodiments of the second aspect of the present application, the single molecule field effect transistor further comprises a substrate; the kind of the substrate is not particularly limited as long as the object of the present application can be achieved, and for example, the substrate may be an atomically flat silicon wafer, mica or sapphire.
In some embodiments of the second aspect of the present application, the graphene gate electrode layer is stripe-shaped and has a width of 5-100nm, and is located directly under the molecular heterojunction.
According to the application, the graphene gate electrode layer can realize accurate patterning, namely the graphene gate electrode layer can be prepared into a width-controllable strip matched with the molecular scale of the compound with the quantum interference effect, the graphene gate electrode layer is strip-shaped, has the width of 5-100nm, is positioned vertically below a molecular heterojunction and between the Bi 2SeO5 dielectric layer and the substrate, thereby realizing accurate regulation and control of a gate electrode on molecules, and reducing the generation of leakage current while reducing the contact area of a gate electrode and a graphene source/drain electrode.
In the present application, the term "atomically flat" means that the roughness of the surface of the material is at the atomic level.
The third aspect of the present application provides a method for manufacturing a single-molecule field effect transistor, comprising the steps of:
1) Preparing a graphene gate electrode layer on a substrate;
2) Preparing a Bi 2SeO5 dielectric layer on the upper surface of the graphene gate electrode layer;
3) Preparing a graphene electrode layer on the upper surface of the Bi 2SeO5 dielectric layer;
4) Constructing a nano gap on the graphene electrode layer to obtain a graphene point electrode, wherein the graphene point electrode comprises a graphene source end electrode and a graphene drain end electrode;
5) Connecting a graphene point electrode with a molecular heterojunction through an amide bond; the molecular heterojunction is composed of any one of the compounds with quantum interference effect provided in the first aspect of the application;
6) And covering the upper surfaces of the graphene point electrode and the molecular heterojunction with an h-BN protective layer to obtain the single-molecule field effect transistor.
The single-molecule field effect transistor is assembled in a two-dimensional lamination way. And the two-dimensional materials are contacted in a van der Waals force mode, for example, van der Waals contact is formed between the Bi 2SeO5 dielectric layer and the graphene gate electrode layer, and van der Waals contact is also formed between the Bi 2SeO5 dielectric layer and the graphene source/drain electrode. The h-BN protective layer is covered on the graphene source/drain electrode and the top of the molecular heterojunction, so that on one hand, the molecular stability is increased through van der Waals contact, on the other hand, the external environment interference is isolated, the air effect is isolated, and the single-molecule field effect transistor device is protected.
By adopting the preparation method, a single-molecule field effect transistor device with good reproducibility can be prepared; based on the single-molecule field effect transistor, a molecular switching device with high switching ratio can be prepared.
In some embodiments of the third aspect of the application, the substrate may be an atomically flat silicon wafer, mica or sapphire.
In step 4), the method for obtaining the graphene point electrode is not particularly limited, so long as the purpose of the present application can be achieved, for example, a graphene electrode layer is formed into a gap of 1-4nm by electron beam Exposure (EBL) and Reactive Ion Etching (RIE), so as to obtain a graphene point electrode, and the graphene point electrode includes a graphene source end electrode and a graphene drain end electrode.
In step 5), the compound with quantum interference effect is in contact with the semi-finished product device obtained in step 4) for self-assembly, and the compound with quantum interference effect is connected with the graphene point electrode (graphene source electrode and graphene drain electrode) through an amide bond (see Angew.chem.int.ed.2013,52,8666 for details).
In some embodiments of the third aspect of the present application, step 5) self-assembling comprises: dissolving the compound with quantum interference effect and a dehydration activator in a solvent to obtain a mixed solution; and then immersing the semi-finished product device obtained in the step 4) into the mixed solution, reacting for 24-48 hours in inert gas under dark condition, taking out, washing and drying.
In some embodiments of the third aspect of the present application, the dehydration activator is selected from at least one of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, or N, N' -diisopropylcarbodiimide; the solvent is selected from at least one of pyridine, dimethyl sulfoxide or trichlorobenzene; the inert gas is argon or nitrogen;
The molar ratio of the compound with quantum interference effect to the dehydration activator is 1 (20-40);
The concentration of the dehydration activator is 2X 10 -3-4×10-3 mol/L.
In some embodiments of the third aspect of the present application, the graphene gate electrode layer, the Bi 2SeO5 dielectric layer, and the graphene electrode layer are obtained by dry transfer or wet transfer.
The specific mode of dry transfer or wet transfer is not particularly limited as long as the purpose of the present application can be achieved, for example, the graphene gate electrode layer, the Bi 2SeO5 dielectric layer, and the graphene electrode layer can be prepared by methods such as mechanical lift-off-dry transfer or Chemical Vapor Deposition (CVD) synthesis-wet transfer.
The dry transfer method can adopt a mechanical stripping mode to obtain the two-dimensional material. Illustratively, a small piece is firstly torn from the two-dimensional material crystal a by using an adhesive tape, and then a new adhesive tape is used for continuously tearing, so that a single-layer or less-layer two-dimensional material a is obtained; adhering the adhesive tape adhered with the two-dimensional material a on a substrate, and tearing the adhesive tape to obtain a thin layer of the two-dimensional material a on the substrate; then, the two-dimensional material b on the adhesive tape is contacted with Polydimethylsiloxane (PDMS) on the top of the glass slide, and when the two-dimensional material b is separated again, a thin layer of the two-dimensional material b is remained on the PDMS; then searching an ultrathin two-dimensional material b on PDMS under a microscope, resolving the spatial positions of the two-dimensional materials by the microscope, adjusting a and b to be completely consistent in the spatial positions by a three-dimensional translation table so as to overlap and contact, at the moment, slightly applying force to a glass slide where b is positioned, adhering the a and the b together, slowly separating the PDMS from the a-b heterojunction, separating the PDMS from the b, and only leaving the a-b heterojunction on the substrate, thereby realizing the further assembly of the two-dimensional material layer.
The wet transfer method takes a graphene gate electrode layer and a Bi 2SeO5 dielectric layer as an example: (1) Firstly, growing a large-area graphene film on a copper foil by using a Chemical Vapor Deposition (CVD) method; (2) Spin-coating polymethyl methacrylate (PMMA) glue on graphene to form a PMMA-graphene-copper foil sandwich structure, putting the structure into ammonium persulfate solution with the concentration of 3% for etching, and transferring the structure into clean deionized water after the copper foil is dissolved so as to remove residual ammonium persulfate in the graphene; (3) Then transferring the graphene-PMMA structure onto a silicon substrate, and removing PMMA glue by soaking in an acetone solution to obtain a graphene gate electrode layer; (4) Growing layered two-dimensional semiconductor bismuth selenide (Bi 2O2 Se) on mica by using a CVD method; (5) Performing high-temperature thermal oxidation operation on a layered two-dimensional semiconductor Bi 2O2 Se on mica (see Nat electronics, 2020,3,473-478) to enable more oxygen atoms to be embedded into a two-dimensional structure, wherein Bi 2O2 Se is controllably converted into Bi 2SeO5 layer by layer; (6) And then, adopting a Polystyrene (PS) auxiliary non-corrosive transfer method to transfer Bi 2SeO5 to the graphene gate electrode layer obtained in the step (3), and specifically: spin-coating PS on Bi 2SeO5 to form a PS-Bi 2SeO5 -mica sandwich structure, and then baking at 80 ℃ for 15min; stripping the PS film and Bi 2SeO5 from mica with the help of deionized water (DI), then placing PS-Bi 2SeO5 on the graphene gate electrode layer obtained in the step (3), baking for 1 hour at 70 ℃, finally washing off PS with toluene, and leaving Bi 2SeO5 on the graphene gate electrode layer to obtain a Bi 2SeO5 dielectric layer; (6) And then annealing at 200-500 ℃ to enable the two-dimensional material interlayer to be more compact.
In some embodiments of the third aspect of the present application, the graphene gate electrode layer has a thickness of 0.7-20nm; the thickness of the Bi 2SeO5 dielectric layer is 1-20nm; the thickness of the h-BN protective layer is 0.7-20nm; the thickness of the graphene source end electrode is 0.7-3nm; the thickness of the graphene drain electrode is 0.7-3nm; the thickness of the molecular heterojunction is 0.7-3nm.
In some embodiments of the third aspect of the present application, the graphene gate electrode layer is strip-shaped and has a width of 5-100nm, and is located directly under the molecular heterojunction.
The quantum interference effect, in particular to the quantum interference cancellation effect, is generated by interference cancellation of electron transmission of different orbits of molecules under specific conditions due to different specific sites of external groups of the molecules, so that lower conductance is generated.
The "switching ratio" is calculated from the ratio of the maximum value of the current to the minimum value of the current in the characteristic curve result of the current variation along with the gate voltage when the bias voltage of the single-molecule field effect transistor is 0.1V.
It should be noted that, the documents cited herein are incorporated herein by reference in their entirety, and are not described in detail herein.
The present application will be specifically described below based on examples, but the present application is not limited to these examples. The experimental materials and methods used in the examples below are conventional materials and methods unless otherwise specified.
The present application records 1 H and 13 CNMR spectra of the compounds on Variance Mercury plus MHz and Bruker ARX 500NMR spectrometers; 1 All chemical shifts of H refer to tetramethylsilane (TMS, δ=0.00 ppm) or deuterated chloroform (Chloroform-d, CDCl 3,δ＝7.26ppm),13 C NMR chemical shift refer to CDCl 3 (δ=77.00 ppm).
The electrical tests to which the application relates were carried out under vacuum (< 1X 10 -4 Pa). Test instrument: agilent 4155C semiconductor tester, ST-500-probe station (Janis Research Company), comprehensive physical testing System (PPMS). The test temperature is precisely regulated and controlled by liquid nitrogen, liquid helium and a heating platform.
And (3) electrical testing: at any temperature in the temperature range of 2K-300K, the voltage applied to the fixed graphene gate electrode strip array is 0V, and the source-drain voltage is applied in the range: -1V, 5mV apart, measuring the current-bias characteristic of a single molecular field effect transistor as a function of bias; the fixed bias is 0.1V, changing the voltage applied across the graphene gate electrode stripe array, ranging: -2V, 10mV apart, measuring the current-gate voltage characteristic of the single-molecule field effect transistor under the control of the gate voltage.
All reactions of the present application were carried out using standard Schlenk techniques under an inert atmosphere of dry solvent and argon or nitrogen.
Example 1 preparation of Single molecule field effect transistor based on Compound A1
(1) Synthesis of compound A1:
1g of m-bromobenzoic acid (compound 1-1,5.11 mmol) was weighed and slowly added dropwise to 20ml of an aqueous solution containing 20% sulfuric acid under nitrogen atmosphere, and refluxed with stirring in an oil bath at 100-200 ℃ for 24 hours; extracting with dichloromethane to obtain an organic phase, and washing the organic phase with saturated sodium bicarbonate solution three times; the organic phase was distilled under reduced pressure, and after sampling with silica gel, column chromatography separation was performed to obtain 0.85g of compound 1-2 (yield 93％).1H NMR(500MHz,Chloroform-d)δ8.02(s,1H),7.91(s,1H),7.65(s,1H).13C NMR(125MHz,CDCl3)δ179.52(s),137.65(s),135.18(s),134.03(s),127.16(s),126.78(s),125.70(s). high resolution mass spectrum (electrospray time of flight mass spectrum) (proton number/charge number) (HRMS (TOF-ESI +) (m/z)) molecular formula C 14H6Br2O2, m/z= 365.87 in positive ion mode.
1G of Compound 1-2 (2.73 mmol) was weighed and slowly added dropwise to 20ml of Tetrahydrofuran (THF) containing 0.15g of activated magnesium turnings (Mg, 6.52 mmol) under nitrogen atmosphere, 0.1g of iodine was added as an initiator, the reaction was initiated by heating the reaction system locally with an electric hair dryer, and the reflux reaction was stirred at room temperature for 2 hours to give Compound 1-3; after the reaction, the system containing the compounds 1-3 is cooled and stirred in an ice water bath, 2.9ml of 3-amino-1-acetone (6.52 mmol) and 10ml of anhydrous diethyl ether mixed solution are slowly added dropwise from a dropping funnel, and the micro-boiling reaction is kept for 1 hour; then, the mixture was cooled in ice water, 50ml of 20% sulfuric acid was added in portions from a dropping funnel to separate layers, the separated aqueous layer was extracted with diethyl ether, then washed with saturated sodium carbonate, finally dried with anhydrous potassium carbonate, and then separated and purified by column chromatography to obtain 0.87g of compound 1-4 (yield 91％).1H NMR(500MHz,Chloroform-d)δ7.79(d,J＝5.0Hz,4H),7.39(s,2H),4.41(s,1H),2.70(s,2H),2.15(s,4H),1.60(s,2H),1.15(s,4H).13C NMR(125MHz,CDCl3)δ181.39(s),149.71(s),133.94(s),133.10(s),131.37(s),125.99(s),124.35(s),73.69(s),40.52(s),39.12(s).HRMS(TOF-ESI+)(m/z) molecular formula C 20H22N2O4, m/z= 354.16).
1G of Compound 1-4 (2.81 mmol), 7ml of trifluoroacetic acid (TFA) and 5ml of MeNO 2 (co-solvent) were weighed into 20ml of tetrahydrofuran, 1ml of triethylsilane (Et 3 SiH,6.31 mmol) was added, and the addition was completed in 5 minutes; stirring at room temperature for reacting for 48 hours to generate precipitate, and filtering; adding 20ml of acetone to dissolve the precipitate, and then adding 30ml of water; filtering, and regulating the pH value of the filtrate to be 8 by ammonia water at 15 ℃ to generate precipitate; the precipitate was collected by filtration, washed with water, dried, and recrystallized from anhydrous diethyl ether to give 0.75g of compound A1 (yield 82％).1H NMR(500MHz,Chloroform-d)δ7.76(s,1H),7.70(s,1H),7.11(s,1H),2.69(s,2H),2.64(s,1H),1.59(s,2H),1.51(s,1H),1.12(s,2H).13C NMR(125MHz,CDCl3)δ182.36(s),150.03(s),133.81(s),132.32(s),131.29(s),126.69(d,J＝10.3Hz),41.32(s),36.45(s),31.33(s),28.01(s).HRMS(TOF-ESI+)(m/z) molecular formula C 20H22N2O2, m/z= 322.17).
(2) Preparation of single molecule field effect transistor comprising compound A1:
Firstly, graphene with the wavelength of 5nm is obtained by using a mechanical stripping mode, namely, repeatedly tearing is carried out by using an adhesive tape; then, using Polydimethylsiloxane (PDMS) as a transfer medium, transferring graphene onto a silicon substrate to be used as a bottom gate electrode; specifically: contacting the graphene on the adhesive tape with PDMS on the top of the glass slide, wherein a graphene thin layer is left on the PDMS during separation; the alignment of graphene and a silicon substrate is regulated through a three-dimensional translation table in a microscope system, at the moment, the glass slide is slightly forced to enable the graphene to be adhered to the silicon substrate, then PDMS is slowly separated, and the graphene is successfully transferred to the silicon substrate, so that a graphene gate electrode layer with the thickness of 5nm is obtained;
Then using Polycarbonate (PC) glue as a transfer medium, and adopting a dry transfer method to transfer the Bi 2SeO5 thin layer onto the graphene gate electrode layer; specifically: firstly, preparing proper Bi 2SeO5 on the surface of a PC on the top of a glass slide 1 by a mechanical stripping method; taking a glass slide 2 with PDMS at the top, taking PC-Bi 2SeO5 out of the glass slide 1 by using a transparent adhesive tape, placing the PC-Bi 2SeO5 on the PDMS with Bi 2SeO5 facing upwards, and forming a PDMS-PC-Bi 2SeO5 structure; almost contacting Bi 2SeO5 with graphene on a silicon substrate through operation of an optical microscope, heating to 60-90 ℃, heating and stretching PC glue at the moment, enlarging the contact area of PC and silicon, completely contacting Bi 2SeO5 with graphene in the gradual moving process, stopping heating, gradually cooling and shrinking the PC glue at the moment, separating the PC glue from the silicon, and combining Bi 2SeO5 on the graphene; finally, slowly separating the PC glue from the Bi 2SeO5 to obtain a Bi 2SeO5 -graphene van der Waals heterostructure, and obtaining a Bi 2SeO5 dielectric layer with the thickness of 10 nm;
Growing a layer of graphene on the surface of the Bi 2SeO5 dielectric layer by using a plasma enhanced chemical vapor deposition (PE-CVD) method to obtain a graphene electrode layer with the thickness of 0.7 nm;
forming a 2nm gap on the graphene electrode layer through electron beam exposure and reactive ion etching to obtain a graphene nano gap point electrode, wherein the graphene nano gap point electrode comprises a graphene source end electrode and a graphene drain end electrode;
Connecting a graphene source end electrode, a graphene drain end electrode and a molecular heterojunction through an amide bond, and specifically:
dissolving a compound A1 and a dehydration activator 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) in pyridine to obtain a mixed solution, wherein the concentration of A1 is 1 multiplied by 10 -4 mol/L, and the concentration of EDCI is 3 multiplied by 10 -3 mol/L; immersing a semi-finished device comprising a graphene gate electrode layer, a Bi 2SeO5 dielectric layer, a graphene source end electrode and a graphene drain end electrode into the mixed solution, reacting for 48 hours in an argon atmosphere under a dark condition, taking out the device from the solution, washing the device with acetone and ultrapure water for three times respectively, and drying the device with nitrogen flow;
Finally, covering an h-BN protective layer with the thickness of 10nm on the top of the device to obtain a single-molecule field effect transistor containing the compound A1; the graphene gate electrode layer is strip-shaped and has a width of 50nm and is positioned vertically under a molecular heterojunction formed by the compound A1.
The single-molecule field effect transistor is composed of a graphene gate electrode layer, a Bi 2SeO5 dielectric layer, a graphene source end electrode, a graphene drain end electrode, a molecular heterojunction formed by a compound A1 and an h-BN protective layer, and the three-dimensional structure diagram is shown in figure 1. Testing a current-bias characteristic curve of a single-molecule field effect transistor which changes along with bias voltage when the gate voltage is 0V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 2; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by a gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 3; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 2 and 3, the single-molecule field effect transistor can obtain 40nA current under the bias of 1V, the switching ratio can reach 400, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 2 preparation of Single molecule field effect transistor based on Compound A2
(1) Synthesis of compound A2:
1g of m-iodobenzoic acid (compound 2-1,4.033 mmol) was weighed and refluxed in 30ml of 20% sulfuric acid aqueous solution under nitrogen atmosphere at 100-200℃for 24 hours; extraction with dichloromethane gave a dichloromethane extract, which was washed three times with saturated sodium bicarbonate solution, and the extract was distilled under reduced pressure and then subjected to column chromatography to give 0.76g of compound 2-2 (yield 82％).1H NMR(500MHz,Chloroform-d)δ8.78(s,1H),8.25(s,1H),7.53(s,1H).13C NMR(125MHz,CDCl3)δ179.70(s),140.87(s),135.48(s),133.65(s),132.07(s),128.03(s),110.76(s).HRMS(TOF-ESI+)(m/z), molecular formula C 14H6I2O2, m/z= 459.85).
1G of compound 2-2 (2.17 mmol), 0.11g of triethylamine (Et 3 N,1.08 mmol), 0.251g of palladium tetrakis (triphenylphosphine) (Pd (PPh 3)4, 0.217 mmol), 0.1g of cuprous iodide (CuI, 0.52 mmol) were weighed into 30ml of diethyl ether, and a 500ml gas bag filled with acetylene (C 2H2, 22.3 mmol) was used to attach the reaction system overnight at room temperature, the reaction was quenched with water and the organic phase was extracted with shaking, washed three times with a saturated sodium chloride solution, and then subjected to column chromatography to give 0.32g of compound 2-3 (yield 57％).1H NMR(500MHz,Chloroform-d)δ8.24(s,1H),7.75(d,J＝15.0Hz,2H),3.07(s,1H).13C NMR(125MHz,CDCl3)δ180.60(s),137.42(s),135.19(s),134.87(s),133.88(s),129.45(s),127.61(s),83.97(s),75.07(s).HRMS(TOF-ESI+)(m/z), molecular formula C 18H8O2, m/z= 256.05).
1G of Compound 2-3 (3.91 mmol), 0.14g of diethylamine (Et 2 NH,1.96 mmol), 0.088g of palladium acetate (Pd (OAc) 2, 0.391 mmol), 0.1g of CuI (0.52 mmol) are weighed out in 30ml of diethyl ether, 0.51g of triphenylphosphine (PPh 3, 1.96 mmol) is added; 10ml of diethyl ether solution in which 1.71g of p-iodoaniline (7.82 mmol) was dissolved was slowly added under nitrogen atmosphere; reflux reaction for 8 hours; adding water to quench the reaction, vibrating and extracting the organic phase, and washing the organic phase for three times by using a saturated sodium chloride solution; then, column chromatography was performed to obtain 1.17g of compound A2 (yield 69％).1H NMR(500MHz,Chloroform-d)δ8.28(s,1H),7.80(s,1H),7.72(s,1H),7.31(s,2H),6.29(s,2H),3.91(s,2H).13C NMR(125MHz,CDCl3)δ180.60(s),148.61(s),137.80(s),135.71(s),134.97(s),132.34(d,J＝12.7Hz),129.62(s),128.38(s),114.79(s),113.64(s),91.51(s),87.34(s).HRMS(TOF-ESI+)(m/z), molecular formula C 30H18N2O2, m/z= 438.14).
(2) Preparation of single molecule field effect transistor comprising compound A2:
The procedure of example 1 was repeated except that the compound A2 was used in place of the compound A1.
Testing a current-bias characteristic curve of the single-molecule field effect transistor which changes along with bias voltage when the gate voltage is 0V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 4; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by a gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 5; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 4 and 5, the single-molecule field effect transistor can obtain 80nA current under the bias of 1V, the switching ratio can reach 1000, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 3 preparation of Compound A3-based Single molecule field effect transistor
(1) Synthesis of compound A3:
1g of 2, 6-lutidine (compound 3-1,9.34 mmol) was weighed, dissolved with 0.02g of dibenzoyl peroxide (BPO, 0.0934 mmol) in 30ml of carbon tetrachloride, 3.3g N-bromosuccinimide (NBS, 18.68 mmol) was slowly added in three portions and reacted under reflux under nitrogen for 8 hours; after the completion, the mixture was frozen in a refrigerator at-20 ℃, filtered to remove the filter residue, and the remaining liquid was subjected to column chromatography after rotary evaporation to obtain 1.04g of compound 3-2 (yield 42％).1H NMR(500MHz,Chloroform-d)δ7.56(s,1H),6.85(s,2H),5.01(s,4H).13C NMR(125MHz,CDCl3)δ157.93(s),138.82(s),116.75(s),30.67(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 7H7Br2 N, m/z= 264.89).
1G of compound 3-2 (3.80 mmol) is weighed, and is dissolved in 20ml of tetrahydrofuran together with 0.2g of magnesium turnings (8 mmol), one iodine particle is added, and the mixture is reacted by heating locally by a baking gun under the nitrogen atmosphere until the iodine particle disappears, and the reaction releases heat automatically; keeping the micro-boiling state and carrying out reflux reaction for 1 hour to generate a compound 3-3; dropwise adding a mixed solution of 5ml of ethylene oxide and 10ml of tetrahydrofuran into a reaction system containing the compounds 3-3 under a nitrogen atmosphere; reflux reaction for 2 hours; after the completion of the reaction, the mixture was subjected to rotary evaporation and purification by column chromatography to obtain 0.68g of Compound 3-4 (yield 93％).1H NMR(500MHz,Chloroform-d)δ7.40(s,2H),7.05(s,7H),3.52(s,10H),3.25(s,7H),2.76(s,8H),1.82(s,13H).13C NMR(125MHz,CDCl3)δ161.22(s),142.14(s),119.82(s),62.80(s),36.11(s),32.75(s).HRMS(TOF-ESI+)(m/z)：, molecular formula C 11H17NO2, m/z= 195.13).
1G of Compound 3-4 (5.2 mmol) was weighed, added to 20ml of tetrahydrofuran solution, and a mixture of 1.12g of phthalimide (7.6 mmol), 0.66g of diethyl azodicarboxylate (DEAD, 3.8 mmol) and 1.0g of triphenylphosphine (3.8 mmol) in 10ml of tetrahydrofuran was added dropwise under nitrogen atmosphere, followed by reflux reaction for 2 hours; then adding a mixed solution of 0.25ml of hydrazine (7.6 mmol) and 5ml of tetrahydrofuran, and carrying out reflux reaction for 16 hours at 0-25 ℃; the reaction solution was washed three times with a saturated sodium chloride solution, and then the organic phase was distilled off in a rotary manner, followed by column chromatography, whereby 0.77g of compound A3 was obtained (yield 76％).1H NMR(500MHz,Chloroform-d)δ7.39(s,4H),7.04(s,16H),2.76(s,18H),2.67(s,16H),2.08(s,32H),1.08(s,31H).13C NMR(125MHz,CDCl3)δ161.22(s),142.14(s),119.82(s),40.82(s),36.31(s),32.57(s).HRMS(TOF-ESI+)(m/z): molecular formula C 11H19N3, m/z= 193.16).
(2) Preparation of single molecule field effect transistor comprising compound A3:
the procedure of example 1 was repeated except that the compound A3 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes along with the bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 6; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by a gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 7; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 6 and 7, the single-molecule field effect transistor can obtain 20nA current under the bias of 1V, the switching ratio can reach 4000, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 4 preparation of Single molecule field effect transistor based on Compound A4
(1) Synthesis of compound A4:
1g of para-iodoaniline (compound 4-1,4.57 mmol) is weighed, 8ml of 18% sodium acetylene (18 wt% with xylene as a dispersing agent) is added under a liquid nitrogen cooling environment, the tube is sealed and reacted in liquid nitrogen for 2 hours; after the reaction, 10ml of water was slowly dropped in an ice bath through a tube, and the organic phase was obtained by extraction and separation, and washed three times with 10ml of 10% hcl, and the washed organic phase was purified by column chromatography after distillation under reduced pressure to obtain 0.41g of compound 4-2 (yield 76.6％).1H NMR(500MHz,Chloroform-d)δ7.27(s,2H),6.30(s,2H),3.79(s,2H),2.82(s,1H).13C NMR(125MHz,CDCl3)δ148.55(s),132.20(s),114.49(s),109.14(s),84.01(s),77.45(s).HRMS(TOF-ESI+)(m/z): molecular formula C 8H7 N, m/z= 117.06).
1G of 2, 6-diiodopyridine (compound 4-3,3.02 mmol) was weighed out with 0.067g of palladium acetate (0.302 mmol), 0.079g of triphenylphosphine (0.302 mmol), 0.29g of cuprous iodide (1.5 mmol), 0.11g of diethylamine (1.5 mmol) were dissolved in 30ml of tetrahydrofuran under nitrogen atmosphere, and a solution of 0.72g of compound 4-2 (6.1 mmol) in 10ml of tetrahydrofuran was slowly added dropwise thereto; reflux reaction for 8 hours; after the completion of the reaction, the reaction was quenched with 50ml of distilled water and subjected to extraction separation, and the organic phase was subjected to column chromatography separation to obtain 0.79g of compound A4 (yield 85％).1H NMR(500MHz,Chloroform-d)δ7.50(s,3H),7.27(s,24H),6.92(s,12H),6.30(s,24H),4.06(s,23H).13C NMR(125MHz,CDCl3)δ148.61(s),142.73(s),140.35(s),132.39(s),128.71(s),114.79(s),113.64(s),90.71(s),86.17(s).HRMS(TOF-ESI+)(m/z):, molecular formula C 21H15N3, m/z= 309.13).
(2) Preparation of single molecule field effect transistor comprising compound A4:
The procedure of example 1 was repeated except that the compound A4 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes along with the bias voltage when the gate voltage is 0V, is tested by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 8; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 9; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 8 and 9, the single-molecule field effect transistor can obtain 20nA current under the bias of 1V, the switching ratio can reach 1700, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 5 preparation of Compound A5-based Single molecule field effect transistor
(1) Synthesis of compound A5:
1g of 1, 3-xylene (compound 5-1,9.4 mmol) was weighed, dissolved with 0.02g of dibenzoyl peroxide (0.094 mmol) in 30ml of carbon tetrachloride, 3.34g N-bromosuccinimide (18.8 mmol) was slowly added in three portions and reacted under reflux under nitrogen for 8 hours; after the completion, the mixture was frozen in a refrigerator at-20℃and filtered to remove the residue, and the remaining liquid was subjected to column chromatography after rotary evaporation to give 1.12g of Compound 5-2 (yield 44％).1H NMR(500MHz,Chloroform-d)δ7.59(s,1H),7.31(s,2H),7.06(s,1H),4.99(s,4H).13C NMR(125MHz,CDCl3)δ140.67(s),128.18(s),126.56(s),124.24(s),31.45(s).HRMS(TOF-ESI+)(m/z): molecular formula C 8H8Br2, m/z= 263.90).
Weighing 1.4g of compound 5-2 (5.15 mmol), dissolving the compound and 0.25g of magnesium turnings (10.5 mmol) in 20ml of tetrahydrofuran, adding one iodine particle, and reacting under nitrogen atmosphere by using a baking gun under local heating until the iodine particle disappears, wherein the reaction releases heat automatically; keeping the micro-boiling state and carrying out reflux reaction for 1 hour to generate a compound 5-3; dropwise adding a mixed solution of 5ml of ethylene oxide and 10ml of tetrahydrofuran into a reaction system containing the compounds 5-3 under a nitrogen atmosphere; reflux reaction for 2 hours; after the completion of the reaction, rotary evaporation was performed, and then purification was performed using column chromatography to obtain 0.88g of compound 5-4 (yield 88％).1H NMR(500MHz,Chloroform-d)δ7.53(s,4H),7.13(s,17H),6.90(s,8H),3.53(s,21H),2.77(s,18H),1.82(s,28H),1.20(s,16H).13C NMR(125MHz,CDCl3)δ142.35(s),130.55(s),129.16(s),125.80(s),62.80(s),34.38(s),33.19(s).HRMS(TOF-ESI+)(m/z): molecular formula C 12H18O2, m/z= 194.13).
1G of Compound 5-4 (5.2 mmol) was weighed, added to 20ml of tetrahydrofuran solution, and a mixture of 1.15g of phthalimide (7.8 mmol), 0.68g of diethyl azodicarboxylate (3.9 mmol) and 1.1g of triphenylphosphine (3.9 mmol) in 10ml of tetrahydrofuran was added dropwise thereto under nitrogen atmosphere, followed by reflux reaction for 2 hours; then adding a mixed solution of 8ml of hydrazine and 5ml of tetrahydrofuran, and carrying out reflux reaction for 16 hours at 0-25 ℃; the reaction solution was washed three times with a saturated sodium chloride solution, and then the organic phase was distilled off, followed by column chromatography to obtain 0.79g of compound A5 (yield 79％).1H NMR(500MHz,Chloroform-d)δ7.53(s,3H),7.13(s,12H),6.90(s,6H),2.68(s,16H),2.63(s,13H),2.09(s,21H),1.16(s,23H).13C NMR(125MHz,CDCl3)δ142.35(s),130.55(s),129.16(s),125.80(s),40.82(s),34.04(s),32.42(s).HRMS(TOF-ESI+)(m/z): molecular formula C 12H20N2, m/z= 192.16).
(2) Preparation of single molecule field effect transistor comprising compound A5:
The procedure of example 1 was repeated except that the compound A5 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes along with the bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 10; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by a gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in FIG. 11; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 10 and 11, the single-molecule field effect transistor can obtain 30nA current under the bias of 1V, the switching ratio can reach 2900, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 6 preparation of Single molecule field effect transistor based on Compound A6
(1) Synthesis of compound A6:
1g of p-iodoaniline (compound 6-1,4.57 mmol) is weighed, 10ml of sodium acetylene (18 wt%, dispersing agent is made from xylene) and 10ml of diethyl ether are added under the cooling environment of liquid nitrogen, the tube is sealed and reacted in liquid nitrogen for 2 hours; after the reaction, 10ml of water was slowly dropped in an ice bath to extract and separate an organic phase, and three extractions were performed with 10ml of 10% hcl, and the organic phase was purified by column chromatography after distillation under reduced pressure to obtain 0.38g of compound 6-2 (yield 71％).1H NMR(500MHz,Chloroform-d)δ7.27(s,2H),6.30(s,2H),3.79(s,2H),2.82(s,1H).13C NMR(125MHz,CDCl3)δ148.55(s),132.20(s),114.49(s),109.14(s),84.01(s),77.45(s).HRMS(TOF-ESI+)(m/z): molecular formula C 8H7 N, m/z= 117.06).
1G of o-diiodobenzene (compound 6-3,3.03 mmol) was weighed out with 0.067g of palladium acetate (0.302 mmol), 0.079g of triphenylphosphine (0.302 mmol), 0.29g of cuprous iodide (1.5 mmol), 0.11g of diethylamine (1.5 mmol) dissolved in 30ml of tetrahydrofuran under nitrogen atmosphere, and a solution of 0.72g of compound 6-2 (6.1 mmol) dissolved in 10ml of tetrahydrofuran was slowly added dropwise thereto; reflux reaction for 8 hours; after the completion of the reaction, the reaction was quenched with 50ml of distilled water and subjected to extraction separation, and the organic phase was subjected to column chromatography separation to obtain 0.72g of compound A6 (yield 80％).1H NMR(500MHz,Chloroform-d)δ7.46(s,15H),7.41(s,9H),7.31(s,28H),7.23(s,4H),6.29(s,31H),3.86(s,30H).13C NMR(125MHz,CDCl3)δ148.61(s),133.50(s),132.39(s),131.69(s),130.09(s),125.41(s),114.79(s),113.64(s),88.76(s),87.89(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 22H16N2, m/z= 308.13).
(2) Preparation of single molecule field effect transistor comprising compound A6:
the procedure of example 1 was repeated except that the compound A6 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 12; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 13; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 12 and 13, the single-molecule field effect transistor can obtain 15nA current under the bias of 1V, the switching ratio can reach 2000, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 7 preparation of Single molecule field effect transistor based on Compound A7
(1) Synthesis of compound A7:
1g of Compound 7-1 (0.011 mol) was weighed, 3.5g of liquid bromine (Br 2, 0.022 mol) and 3.2g of ferric bromide (FeBr 3, 0.011 mol) were added, and the mixture was heated to 300℃in an oil bath under nitrogen atmosphere and reacted for 16 hours under reflux; after the reaction was completed, water was added to quench, and the organic phase was washed three times with 10ml of 10% hcl solution; the obtained organic phase was distilled under reduced pressure and then subjected to column chromatography to obtain 0.63g of Compound 7-2 (yield 22%). The nmr hydrogen spectrum and mass spectrum characterization data of this example were measured using r=ch 3 to determine the molecular formula C 6H5Br2 N, m/z=250.88 for ,1H NMR(500MHz,Chloroform-d)δ8.68(s,2H),2.45(s,3H).13C NMR(125MHz,CDCl3)δ152.19(s),150.07(s),120.77(s),23.13(s).HRMS(TOF-ESI+)(m/z)：.
1G of Compound 7-2 (3.99 mmol) was weighed, dissolved in 10ml of tetrahydrofuran solution, and a tetrahydrofuran solution in which 1.7g of 3-amino-propylzinc (II) chloride was dissolved was slowly dropped in succession under nitrogen atmosphere; 15ml of Dimethylformamide (DMF) dissolved with 0.8g of 3-chloropropylamine (8 mmol) and 0.047g of tetrakis (triphenylphosphine) palladium (Pd (PPh 3)4, 0.04 mmol) were reacted at reflux temperature 153℃for 16 hours, after the reaction was completed 20ml of water were used for extraction and the organic phase was washed three times with 10% HCl solution, and the obtained organic phase was subjected to rotary evaporation and column chromatography to give 0.79g of compound 7-3 (yield 94％).1H NMR(500MHz,Chloroform-d)δ8.43(s,1H),2.68(s,1H),2.63(s,1H),2.29(s,1H),2.09(s,1H),1.11(s,2H).13C NMR(125MHz,CDCl3)δ147.09(s),140.61(s),136.38(s),40.82(s),31.66(s),30.53(s),16.88(s).HRMS(TOF-ESI+)(m/z)：, formula C 12H21N3, m/z= 207.17).
1G of Compound 7-3 (4.82 mmol) was weighed into a 20ml tetrahydrofuran solution, and a 10ml tetrahydrofuran solution in which 0.68g of n-bromobutane (4.82 mmol) was dissolved was added dropwise under nitrogen atmosphere; reflux reaction for 8 hours; the aqueous phase was retained after extraction with 10ml of water and distillation under reduced pressure gave a solid product, namely 0.66g of compound 7-4 (yield 39％).1H NMR(500MHz,Chloroform-d)δ8.31(s,10H),3.17(s,7H),2.68(s,15H),2.63(s,13H),2.27(s,15H),2.09(s,13H),2.04(s,11H),1.25(s,6H),1.10(s,20H),0.89(s,8H).13C NMR(125MHz,CDCl3)δ146.14(s),145.57(s),139.22(s),62.52(s),40.82(s),31.66(s),30.36(d,J＝6.4Hz),19.62(s),16.88(s),14.00(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 16H30BrN3, m/z= 343.16.
1G of Compound 7-4 (2.91 mmol) and 0.07g of sodium hydride (2.91 mmol) were weighed into 15ml of dimethylformamide solution, and 5ml of dimethylformamide solution in which 0.2g of cyclopentadiene (2.91 mmol) was dissolved was slowly added dropwise under nitrogen atmosphere; after 16 hours at room temperature, the reaction was quenched with water, and the organic phase was washed three times with 10ml of 10% hcl solution, and was subjected to column chromatography after rotary evaporation to give 0.72g of compound A7 (yield 95％).1H NMR(500MHz,Chloroform-d)δ8.31(s,15H),7.90(s,4H),7.38(s,15H),2.68(s,18H),2.63(s,17H),2.27(s,22H),2.09(s,23H),1.21(s,29H).13C NMR(125MHz,CDCl3)δ138.84(s),138.31(s),137.40(s),133.79(s),132.86(s),131.30(s),117.31(d,J＝15.0Hz),41.19(s),31.65(s),30.06(s),16.49(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 17H24N2, m/z= 256.19).
(2) Preparation of single molecule field effect transistor comprising compound A7:
the procedure of example 1 was repeated except that the compound A7 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 14; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 15; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 14 and 15, the single-molecule field effect transistor can obtain 100nA current under the bias of 1V, the switching ratio can reach 2700, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 8 preparation of Single molecule field effect transistor based on Compound A8
(1) Synthesis of compound A8:
1g of Compound 8-1 (2.90 mmol) was weighed, dissolved together with 0.53g of iodobutane (2.90 mmol) in 20ml of tetrahydrofuran, and reacted under reflux with heating under nitrogen atmosphere for 16 hours; after the reaction was completed, 20ml of water was added to quench the reaction and extract the reaction mixture, and the aqueous phase was retained and rotary evaporation was performed to obtain a solid product, namely, 0.88g of Compound 8-2 (yield: 75%). The nmr hydrogen spectrum and mass spectrum characterization data of this example were measured using r=ch 3 to determine the molecular formula C 10H14I2N+, m/z= 401.92 of ,1H NMR(500MHz,Chloroform-d)δ9.35(s,10H),3.02(s,5H),2.43(s,15H),2.03(s,4H),1.25(s,6H),0.89(s,8H).13C NMR(125MHz,CDCl3)δ157.81(s),156.23(s),66.30(s),62.52(s),30.33(s),20.76(s),19.62(s),14.00(s).HRMS(TOF-ESI+)(m/z)：.
1G of Compound 8-2 (2.48 mmol) and 0.03g of sodium hydride (1.24 mmol) were weighed and dissolved in 15ml of dimethylformamide, 5ml of dimethylformamide solution in which 0.17g of cyclopentadiene (2.48 mmol) was dissolved was slowly dropped under nitrogen atmosphere, the reaction was carried out at room temperature for 16 hours, water was added to quench the reaction, extraction was carried out, and the organic phase was washed three times with 10% HCl solution, and the organic phase was separated by column chromatography after distillation under reduced pressure to give 0.76g of Compound 8-3 (yield 77％).1H NMR(500MHz,Chloroform-d)δ8.31(s,4H),7.90(s,1H),7.38(s,4H),2.43(s,6H).13C NMR(125MHz,CDCl3)δ144.24(s),139.77(s),132.86(s),128.07(s),126.60(s),118.50(d,J＝15.0Hz),21.50(s).HRMS(TOF-ESI+)(m/z)： formula C 11H8I2, m/z= 393.99).
1G of Compound 8-3 (2.52 mmol) was weighed out, and 0.057g of palladium acetate (0.252 mmol), 0.066g of triphenylphosphine (0.252 mmol), 0.24g of cuprous iodide (1.25 mmol), 0.09g of diethylamine (1.25 mmol) was dissolved in 30ml of tetrahydrofuran under nitrogen atmosphere, and a solution of p-acetylene aniline 0.6g (5.04 mmol) in 10ml of tetrahydrofuran was slowly added dropwise thereto; reflux reaction for 8 hours; after the completion of the reaction, the reaction was quenched with 50ml of distilled water and subjected to extraction separation, and the organic phase was subjected to rotary evaporation and then column chromatography to obtain 0.90g of compound A8 (yield 90％).1H NMR(500MHz,Chloroform-d)δ8.31(s,4H),7.90(s,1H),7.33(d,J＝55.0Hz,12H),6.30(s,8H),3.66(s,8H),2.43(s,6H).13C NMR(125MHz,CDCl3)δ154.61(s),148.61(s),142.86(s),135.86(s),132.86(s),132.39(s),127.95(s),123.13(s),119.85(d,J＝15.0Hz),114.79(s),113.64(s),103.78(s),86.18(s),17.64(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 27H20N2, m/z= 372.16).
(2) Preparation of single molecule field effect transistor comprising compound A8:
the procedure of example 1 was repeated except that the compound A8 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 16; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 17; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 16 and 17, 200nA current can be obtained by the single-molecule field effect transistor under the bias of 1V, the switching ratio can reach 3000, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 9 preparation of Single molecule field effect transistor based on Compound A9
(1) Synthesis of compound A9:
1g of Compound 9-1 (3.01 mmol) was weighed and dissolved in 20ml of tetrahydrofuran solvent together with 1.07g N-bromosuccinimide (6.02 mmol) and 0.007g benzoyl peroxide (0.0301 mmol); reacting for 8 hours in nitrogen atmosphere; after completion of the reaction, the reaction was quenched with 20ml of water, the organic phase was washed three times with 10ml of 10% HCl solution, and the organic phase was separated by column chromatography after distillation under reduced pressure to give 0.77g of Compound 9-2 (yield 52%). The nmr hydrogen spectrum and mass spectrum characterization data of this example were measured using r=ch 3 to determine the molecular formula C 26H18Br2, m/z= 489.98 of ,1H NMR(500MHz,Chloroform-d)δ8.22(d,J＝69.8Hz,2H),7.55(s,1H),7.47(s,1H),5.45(s,2H),2.73(s,3H).13C NMR(125MHz,CDCl3)δ140.64(s),130.27(s),130.04(s),129.44(s),128.07(s),126.18(d,J＝19.6Hz),121.22(s),117.85(d,J＝17.3Hz),116.88(s),30.67(s),18.61(s).HRMS(TOF-ESI+)(m/z)：.
1G of compound 9-2 (2.05 mmol) is weighed, and is dissolved in 20ml of tetrahydrofuran together with 0.1g of magnesium turnings (4.1 mmol), one iodine particle is added, and the mixture is reacted by heating locally by a baking gun under the nitrogen atmosphere until the iodine particle disappears, and the reaction releases heat automatically; reflux reaction is carried out for 1 hour under the micro-boiling state to obtain a compound 9-3; dropwise adding a mixed solution of 5ml of ethylene oxide and 10ml of tetrahydrofuran into a reaction system containing the compound 9-3 under a nitrogen atmosphere; reflux reaction for 2 hours; after the completion of the reaction, rotary evaporation was performed, and then purification was performed using column chromatography to obtain 0.76g of compound 9-4 (yield 88％).1H NMR(500MHz,Chloroform-d)δ8.15(s,5H),7.92(s,5H),7.55(s,5H),7.47(s,5H),3.53(s,9H),3.07(s,5H),2.73(s,15H),1.84(s,7H),1.49(s,5H).13C NMR(125MHz,CDCl3)δ140.92(s),132.20(s),131.91(s),129.70(s),128.07(s),126.24(d,J＝5.0Hz),120.54(s),119.92(s),118.40(s),116.50(s),62.80(s),33.06(s),32.70(s),18.61(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 30H28O2, m/z= 420.21).
1G of Compound 9-4 (2.38 mmol) was weighed and added to 20ml of tetrahydrofuran solution, and a mixture of 0.56g of phthalimide (3.8 mmol), 0.33g of diethyl azodicarboxylate (1.9 mmol) and 0.50g of triphenylphosphine (1.9 mmol) in 10ml of tetrahydrofuran was added dropwise thereto under nitrogen atmosphere and reacted under reflux for 2 hours; then adding a mixed solution of 8ml of hydrazine and 5ml of tetrahydrofuran, and reacting for 16 hours at the temperature of 0-20 ℃; the reaction solution was washed three times with a saturated sodium chloride solution, and the obtained organic phase was subjected to column chromatography after being distilled off, whereby 0.79g of compound A9 was obtained (yield 79％).1H NMR(500MHz,Chloroform-d)δ8.10(s,1H),7.87(s,1H),7.50(s,1H),7.42(s,1H),3.05(s,1H),2.71(s,3H),2.66(s,1H),2.10(s,1H),1.49(s,2H).13C NMR(125MHz,CDCl3)δ140.92(s),132.20(s),131.91(s),129.70(s),128.07(s),126.24(d,J＝5.0Hz),120.54(s),119.92(s),118.40(s),116.50(s),40.82(s),32.21(d,J＝16.4Hz),18.61(s).HRMS(TOF-ESI+)(m/z): molecular formula C 30H30N2, m/z= 418.24).
(2) Preparation of single molecule field effect transistor comprising compound A9:
The procedure of example 1 was repeated except that compound A9 was used instead of compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 18; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 19; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 18 and 19, the single-molecule field effect transistor can obtain 50nA current under the bias of 1V, the switching ratio can reach 600, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 10 preparation of Compound A10-based Single molecule field effect transistor
(1) Synthesis of compound a 10:
1g of compound 10-1 (1.80 mmol) was weighed out with 0.05g of palladium acetate (0.18 mmol), 0.05g of triphenylphosphine (0.18 mmol), 0.17g of cuprous iodide (0.9 mmol), 0.06g of diethylamine (0.9 mmol) dissolved in 30ml of tetrahydrofuran under nitrogen atmosphere, and then 10ml of tetrahydrofuran solution in which 0.46g (3.85 mmol) of p-acetylene aniline was dissolved was slowly added dropwise; reflux reaction for 8 hours; after the completion of the reaction, the reaction was quenched with 50ml of distilled water and subjected to extraction separation, and the obtained organic phase was subjected to rotary evaporation and then column chromatography to obtain 0.90g of compound a10 (yield 94％).1H NMR(500MHz,Chloroform-d)δ8.54(s,4H),8.21(s,4H),7.71(s,4H),7.47(s,2H),7.31(s,9H),6.29(s,8H),4.14(s,8H),2.73(s,12H).13C NMR(125MHz,CDCl3)δ148.61(s),135.27(s),134.71(s),132.98(s),132.39(s),128.39(s),127.21(s),126.43(s),125.70(s),124.31(s),123.96(s),122.88(s),121.81(s),114.79(s),113.64(s),92.89(s),85.17(s),18.61(s).HRMS(TOF-ESI+)(m/z): molecular formula C 40H26N2, m/z= 534.21).
(2) Preparation of single molecule field effect transistor comprising compound a 10:
the procedure of example 1 was repeated except that compound A10 was used instead of compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 20; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by a gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, wherein the result is shown in figure 21; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 20 and 21, the single-molecule field effect transistor can obtain 10nA current under the bias of 1V, the switching ratio can reach 250, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 11 preparation of Compound A11-based Single molecule field effect transistor
(1) Synthesis of compound a 11:
1g of m-methylbenzoic acid (compound 11-1,7.46 mmol) is weighed, dissolved in 10ml of tetrahydrofuran solution together with 0.1g of zinc powder (1.5 mmol) and 0.29g of titanium tetrachloride (1.5 mmol) under nitrogen atmosphere, sealed under low temperature environment, and then reacted for 8 hours at 0-85 ℃; after the completion of the reaction, the tube was opened, slowly added to 10ml of water and the extract was separated to obtain an organic phase, the organic phase was washed with 10ml of saturated sodium chloride solution, the organic phase was distilled under reduced pressure, and then subjected to column chromatography to obtain 0.75g of compound 11-2 (yield 92％).1H NMR(500MHz,Chloroform-d)δ7.43(s,2H),7.28(s,2H),7.19(s,1H),6.93(d,J＝20.0Hz,4H),2.42(s,6H).13C NMR(125MHz,CDCl3)δ139.04(s),137.08(s),130.15(s),129.89(s),128.84(s),128.52(s),125.83(s),21.23(s).HRMS(TOF-ESI+)(m/z): molecular formula C 16H16, m/z= 208.13).
1G of Compound 11-2 (4.80 mmol) was weighed and dissolved in 20ml of tetrahydrofuran solvent together with 1.71g N-bromosuccinimide (9.60 mmol) and 0.01g benzoyl peroxide (0.0480 mmol); reacting for 8 hours in nitrogen atmosphere; after the completion of the reaction, the reaction was quenched with 20ml of water and the separated liquid was extracted to obtain an organic phase, which was washed three times with 10ml of 10% hcl solution, distilled under reduced pressure, and then separated by column chromatography to obtain 0.71g of compound 11-3 (yield 40％).1H NMR(500MHz,Chloroform-d)δ7.45(d,J＝50.0Hz,6H),7.27(s,2H),7.19(s,3H),6.95(s,3H),4.78(s,6H).13C NMR(125MHz,CDCl3)δ143.44(s),135.79(s),128.84(s),128.37(s),128.10(d,J＝18.7Hz),124.39(s),31.45(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 16H14Br2, m/z= 365.94).
1G of compound 11-3 (2.73 mmol) is weighed, and is dissolved in 20ml of tetrahydrofuran together with 0.14g of magnesium turnings (5.5 mmol), one iodine particle is added, and the mixture is reacted by heating locally by a baking gun under the nitrogen atmosphere until the iodine particle disappears, and the reaction releases heat automatically; reflux reaction is carried out for 1 hour under the micro-boiling state to generate a compound 11-4; dropwise adding a mixed solution of 5ml of ethylene oxide and 10ml of tetrahydrofuran into a reaction system containing the compound 11-4 under a nitrogen atmosphere; reflux reaction for 2 hours; after the completion of the reaction, rotary evaporation was performed, and purification was performed using column chromatography to obtain 0.73g of compound 11-5 (yield 90％).1H NMR(500MHz,Chloroform-d)δ7.43(s,4H),7.32(s,4H),7.24(s,2H),7.08(s,5H),6.95(s,4H),3.53(s,5H),2.77(s,4H),1.82(s,7H),1.24(s,4H).13C NMR(125MHz,CDCl3)δ144.38(s),138.74(s),131.95(s),130.57(s),128.84(s),128.57(s),125.13(s),62.80(s),34.38(s),33.19(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 20H24O2, m/z= 296.41).
1G of Compound 11-5 (3.37 mmol) was weighed and added to 20ml of tetrahydrofuran solution, and a mixture of 0.78g of phthalimide (5.1 mmol), 0.89g of diethyl azodicarboxylate (5.1 mmol) and 0.66g of triphenylphosphine (2.5 mmol) in 10ml of tetrahydrofuran was added dropwise to the system under nitrogen atmosphere, followed by reflux reaction for 2 hours; then adding a mixed solution of 8ml of hydrazine and 5ml of tetrahydrofuran, and reacting for 12 hours at the temperature of 0-20 ℃; after the reaction solution was washed three times with a saturated sodium chloride solution, the obtained organic phase was subjected to rotary evaporation and then to column chromatography, whereby 0.79g of compound a11 was obtained (yield 79％).1H NMR(500MHz,Chloroform-d)δ7.38(d,J＝55.0Hz,61H),7.27(s,7H),7.24(s,15H),7.08(s,42H),6.95(s,26H),2.68(s,31H),2.63(s,40H),2.09(s,60H),1.10(s,58H).13C NMR(125MHz,CDCl3)δ144.38(s),138.74(s),131.95(s),130.57(s),128.84(s),128.57(s),125.13(s),40.82(s),34.04(s),32.42(s).HRMS(TOF-ESI+)(m/z)： molecular formula C 20H26N2, m/z= 294.21).
(2) Preparation of single molecule field effect transistor comprising compound a 11:
The procedure of example 1 was repeated except that the compound A11 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 22; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in figure 23; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 22 and 23, the single-molecule field effect transistor can obtain 40nA current under the bias of 1V, the switching ratio can reach 170, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Example 12 preparation of Single molecule field effect transistor based on Compound A12
(1) Synthesis of compound a 12:
1g of m-iodobenzoic acid (compound 12-1,4.06 mmol) is weighed, dissolved in 10ml of tetrahydrofuran solution together with 0.05g of zinc powder (0.81 mmol) and 0.15g of titanium tetrachloride (0.81 mmol) under nitrogen atmosphere, sealed under low temperature environment, and then reacted for 8 hours at 0-85 ℃; after the completion of the reaction, the tube was opened, slowly added to 10ml of water and subjected to extraction and separation to obtain an organic phase, the organic phase was washed with 10ml of saturated sodium chloride solution, the organic phase was distilled under reduced pressure, and then subjected to column chromatography to obtain 0.75g of compound 12-2 (yield 84％).1H NMR(500MHz,Chloroform-d)δ7.88(s,2H),7.61(s,2H),7.52(s,2H),7.09(s,1H),6.95(s,2H).13C NMR(125MHz,CDCl3)δ140.44(s),139.09(s),137.77(s),130.98(s),129.85(s),128.84(s),95.66(s).HRMS(TOF-ESI+)(m/z): molecular formula C 14H10I2, m/z= 431.89).
1G of Compound 12-2 (2.32 mmol) was dissolved in 30ml of tetrahydrofuran under nitrogen atmosphere with 0.05g of palladium acetate (0.23 mmol), 0.06g of triphenylphosphine (0.23 mmol), 0.23g of cuprous iodide (1.2 mmol), 0.08g of diethylamine (1.2 mmol), and a solution of p-acetylene aniline 0.55g (4.7 mmol) in 10ml of tetrahydrofuran was slowly added dropwise thereto; reflux reaction for 8 hours; after the completion of the reaction, the reaction was quenched with 50ml of distilled water and subjected to extraction separation to obtain an organic phase, which was distilled off in a rotary manner, followed by column chromatography to obtain 0.89g of compound a12 (yield 91％).1H NMR(500MHz,Chloroform)δ7.90(s,2H),7.45(d,J＝10.0Hz,5H),7.38(s,1H),7.31(s,4H),6.95(s,2H),6.29(s,4H),3.87(s,4H).13C NMR(125MHz,CDCl3)δ148.61(s),136.27(s),132.39(s),131.10(s),130.02(s),128.91(d,J＝16.6Hz),128.51(s),127.76(s),114.79(s),113.64(s),88.76(s),87.89(s).HRMS(TOF-ESI+)(m/z): molecular formula C 30H22N2, m/z= 410.22.
(2) Preparation of single molecule field effect transistor comprising compound a 12:
the procedure of example 1 was repeated except that the compound A12 was used in place of the compound A1.
The current-bias characteristic curve of the single-molecule field effect transistor, which changes with bias voltage when the gate voltage is 0V, is tested by using an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 24; testing a current-gate voltage characteristic curve of the single-molecule field effect transistor regulated by the gate voltage when the bias voltage is 0.1V by adopting an Agilent 4155C semiconductor tester and an ST-500-probe station, and the result is shown in FIG. 25; the temperature dependence is tested by using a comprehensive physical property testing system, the results are consistent in the range of 2-300K, and according to fig. 24 and 25, the single-molecule field effect transistor can obtain 35nA current under the bias of 1V, the switching ratio can reach 400, so that the obtained single-molecule field effect transistor has strong regulation and control capability on the molecular conductivity characteristics and can exist stably in an air environment for a long time.
Yield calculation:
Yield = actual synthetic product mass/theoretical synthetic product mass x 100%.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (14)

1. A compound with quantum interference effect has a structural formula shown in a formula A:
H2N-R2-R1-R2-NH2
Formula A;
Wherein R 1 is selected from formula IV;
R 2 is selected from- (CH 2)m) -or M is an integer of 1 to 6;
r is selected from CH 3(CH2)n, and n is an integer of 0-5.
2. The compound having a quantum interference effect according to claim 1, wherein the compound having a quantum interference effect is selected from any one of formulas A7 to A8:
3. a single molecule field effect transistor comprising any one of the compounds having quantum interference effects of claim 1.
4. The single molecule field effect transistor of claim 3, wherein the single molecule field effect transistor further comprises a graphene gate electrode layer, a Bi 2SeO5 dielectric layer, a graphene source terminal electrode, a graphene drain terminal electrode, a molecular heterojunction, and an h-BN protective layer; the molecular heterojunction is composed of the compound with quantum interference effect.
5. The single molecule field effect transistor of claim 4, wherein the graphene gate electrode layer has a thickness of 0.7-20nm; the thickness of the Bi 2SeO5 dielectric layer is 1-20nm; the thickness of the h-BN protective layer is 0.7-20nm; the thickness of the graphene source end electrode is 0.7-3nm; the thickness of the graphene drain electrode is 0.7-3nm; the thickness of the molecular heterojunction is 0.7-3nm.
6. The single-molecule field effect transistor of claim 4, wherein the single-molecule field effect transistor further comprises a substrate; the substrate is an atomically flat silicon wafer, mica or sapphire.
7. The single molecule field effect transistor of claim 4, wherein the graphene gate electrode layer is stripe-shaped with a width of 5-100nm, located vertically directly below the molecular heterojunction.
8. A method of fabricating a single molecule field effect transistor comprising the steps of:
1) Preparing a graphene gate electrode layer on a substrate;
2) Preparing a Bi 2SeO5 dielectric layer on the upper surface of the graphene gate electrode layer;
3) Preparing a graphene electrode layer on the upper surface of the Bi 2SeO5 dielectric layer;
4) Constructing a nano gap on the graphene electrode layer to obtain a graphene point electrode, wherein the graphene point electrode comprises a graphene source end electrode and a graphene drain end electrode;
5) Connecting a graphene point electrode with a molecular heterojunction through an amide bond; the molecular heterojunction is composed of any one of the compounds having quantum interference effect as claimed in claim 1;
6) And covering the upper surfaces of the graphene point electrode and the molecular heterojunction with an h-BN protective layer to obtain the single-molecule field effect transistor.
9. The method of manufacturing according to claim 8, wherein step 4) includes: and constructing a gap of 1-4nm by using the graphene electrode layer through electron beam exposure and reactive ion etching to obtain a graphene point electrode, wherein the graphene point electrode comprises a graphene source end electrode and a graphene drain end electrode.
10. The method of manufacturing according to claim 8, wherein step 5) comprises: dissolving the compound with quantum interference effect and a dehydration activator in a solvent to obtain a mixed solution; and then immersing the semi-finished product device obtained in the step 4) into the mixed solution, reacting for 24-48 hours in inert gas under dark condition, taking out, washing and drying.
11. The production method according to claim 10, wherein the dehydration activator is at least one selected from 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, or N, N' -diisopropylcarbodiimide; the solvent is selected from at least one of pyridine, dimethyl sulfoxide or trichlorobenzene; the inert gas is argon or nitrogen;
The molar ratio of the compound with quantum interference effect to the dehydration activator is 1 (20-40);
The concentration of the dehydration activator is 2X 10 -3-4×10-3 mol/L.
12. The preparation method of claim 8, wherein the graphene gate electrode layer, the Bi 2SeO5 dielectric layer and the graphene electrode layer are obtained by means of dry transfer or wet transfer.
13. The manufacturing method according to claim 8, wherein the thickness of the graphene gate electrode layer is 0.7-20nm; the thickness of the Bi 2SeO5 dielectric layer is 1-20nm; the thickness of the h-BN protective layer is 0.7-20nm; the thickness of the graphene source end electrode is 0.7-3nm; the thickness of the graphene drain electrode is 0.7-3nm; the thickness of the molecular heterojunction is 0.7-3nm.
14. The preparation method of claim 8, wherein the graphene gate electrode layer is strip-shaped and has a width of 5-100nm and is located vertically under the molecular heterojunction.
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