WO2009127896A1 - Synthèse d’un réseau monocouche covalent ordonnée sur une surface - Google Patents

Synthèse d’un réseau monocouche covalent ordonnée sur une surface Download PDF

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Publication number
WO2009127896A1
WO2009127896A1 PCT/IB2008/002342 IB2008002342W WO2009127896A1 WO 2009127896 A1 WO2009127896 A1 WO 2009127896A1 IB 2008002342 W IB2008002342 W IB 2008002342W WO 2009127896 A1 WO2009127896 A1 WO 2009127896A1
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Prior art keywords
polyfunctional
network
process according
boronic acid
linked
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PCT/IB2008/002342
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English (en)
Inventor
Nikolas Zwaneveld
Rémy PAWLAK
Louis Porte
Daniel Catalin
Denis Bertin
Mathieu Abel
Didier Gigmes
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Universite D'aix-Marseille I
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Priority to PCT/IB2008/002342 priority Critical patent/WO2009127896A1/fr
Publication of WO2009127896A1 publication Critical patent/WO2009127896A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the present invention relates to the field of synthesizing covalent two- dimensional monolayer networks on a surface using at least one reactant.
  • the present invention aims to discover a process of formation of a surface covalent network on a surface, to achieve complete monolayer coverage with the required stability for further usage and synthesis.
  • the present invention is based on the formation of a novel two- dimensional ordered covalent porous network across a surface, and comprising an organized boroxine- or boronate- linked organic structure that can be formed from the deposition of boronic acids or esters thereof, alone or combined with complementary reactants.
  • boroxine- or boronate- linked organic structure that can be formed from the deposition of boronic acids or esters thereof, alone or combined with complementary reactants.
  • one embodiment of the invention relates to a process for synthesizing a covalent ordered network onto a surface, comprising: depositing onto said surface a polyfunctional boronic acid or a boronate ester, and reacting the polyfunctional boronic acid or boronate ester with a second reactant so as to obtain a boroxine-linked or a boronate- linked organic monolayer network.
  • the process comprises reacting the polyfunctional boronic acid with itself as second reactant.
  • the process comprises reacting the polyfunctional boronic acid with another polyfunctional boronic acid.
  • the process comprises reacting the polyfunctional boronic acid with a second reactant selected from the group consisting of polyfunctional diol, polyfunctional diamine, polyfunctional amino alcohol, polyfunctional thiol. In one embodiment, the process comprises reacting a boronate ester with a second reactant selected from the group consisting of polyfunctional diol, polyfunctional diamine, polyfunctional amino alcohol, polyfunctional thiol.
  • the process comprises depositing the second reactant onto said surface prior to the polyfunctional boronic acid so as to prevent the polyfunctional boronic acid from reacting with itself.
  • the process comprises co-depositing the polyfunctional boronic acid or boronate ester and the second reactant at the same time onto said surface.
  • the process comprises depositing the polyfunctional boronic acid or the boronate ester and the second reactant under ultra high vacuum and by sublimation of the reactants.
  • the process comprises adding functional substituents to the reactants prior to deposition onto said surface.
  • the process comprises a further step of incorporating heterocyclic macrocycles into the network.
  • the process comprises a further step of selectively depositing a material in pores of the porous covalent organic network.
  • the reactants are deposited onto an orientated crystalline surface.
  • One embodiment of the invention also relates to a process of manufacturing a network of nanoparticles onto a surface, comprising: synthesizing a porous covalent organic network onto the surface according to the above-described process, and selectively depositing a material in pores of the porous covalent organic network.
  • the process comprises a further step of removing the network.
  • One embodiment of the invention also relates to a covalent ordered monolayer on a surface, comprising a boroxine-linked or a boronate-linked network and having a two dimensional nano-meter scale porous structure.
  • the boroxine-linked or a boronate-linked network comprises a predominance of pores having a hexagonal structure.
  • Fig. 1 shows an example of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid, resulting in a boroxine-linked network;
  • Fig. 2 shows an example of a covalent ordered organic network formed from a 1 ,3,5-benzenetriboronic acid, resulting in a boroxine-linked network;
  • Fig. 3 shows an example of a covalent ordered organic network formed from 2,3,6,7, 10,11-hexahydroxytriphenylene and 1 ,4- benzenediboronic acid, resulting in a boronic ester linked network;
  • Fig. 4 shows an example of a covalent ordered organic network formed from a reaction of boronic acid and functionalized reactants, resulting in a boronic ester-linked network
  • Fig. 5 shows an example of a covalent ordered organic network formed from the reaction of a heterocyclic boronic ester of 1 ,4- benzenediboronic acid and 2,3,6,7,10,11-hexahydroxytriphenylene, resulting in a boronic ester linked network;
  • Fig. 6a shows a measured profile and pore size of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid on Ag(111 );
  • Fig. 6b shows a measured vertical height of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid on Ag(111 );
  • Fig. 7 shows a DFT modeled structure of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid
  • Fig. 8a shows a measured profile and pore size of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid and 2,3,6,7,10,11-hexahydroxytriphenylene on Ag(111 );
  • - Fig. 8b shows a measured vertical height of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid and 2,3,6,7,10,11- hexahydroxytriphenylene on Ag(111 ); and - Fig. 9 shows a DFT modeled structure of a covalent ordered organic network formed from 1 ,4-benzenediboronic acid and 2,3,6,7,10,11- hexahydroxytriphenylene.
  • a covalently linked, ordered monolayer network on a surface can be formed from the deposition and reaction of boronic acids with themselves or with a polyfunctional secondary reactant or by the reaction of boronic esters with a polyfunctional second reactant.
  • the resulting network is covalently bonded, thus providing remarkable stability and enhanced functionality.
  • the characteristics and properties of the resulting network may be varied and altered by changing the reactants and by incorporating functional groups into the reactants.
  • the ordered monolayer network is covalently bonded and thus stable under standard atmospheric conditions. Additionally the network can by readily hydrolyzed in a humid atmosphere providing a ready method for removing the network after its utilization if this is desired. Embodiments of a process for producing such a covalent ordered organic network will be described hereinafter in further detail.
  • a boroxine-linked network is produced using an anhydride formation process.
  • a boronic acid such as 1 ,4-benzenediboronic acid or BDBA is reacted with itself and generates a self-assembled, ordered, stable, monolayer network as shown in Fig. 1 and as described below:
  • the BDBA is purified then loaded into a sublimation equipment, which in this example is a UHV (Ultra High Vacuum) sublimation equipment, and is deposited onto a flat surface, for instance a mono-crystalline surface (gold, silver, nickel, graphite etc.).
  • a sublimation equipment which in this example is a UHV (Ultra High Vacuum) sublimation equipment, and is deposited onto a flat surface, for instance a mono-crystalline surface (gold, silver, nickel, graphite etc.).
  • an orientated crystalline Ag surface is prepared by repeated cycles of argon sputtering (800V, 1 ⁇ A) and annealing at 700 K.
  • the BDBA is purified by careful vacuum sublimation at 445K and approximately 10 Pascal.
  • the BDBA is then loaded into the sublimation equipment, for instance PVD equipment (Physical Vapor Deposition).
  • the BDBA is then out-gassed in vacuum and evaporated from a heated molybdenum crucible evaporator under ultra-high vacuum conditions (1x10 7 Pascal) onto the Ag surface.
  • the deposition rate is about 0.5 monolayer per minute (one monolayer corresponding to a complete layer of the dense molecular phase).
  • the BDBA evaporator temperature may be varied between 370 and 460 K. During the deposition the sample can be kept either at room temperature (298K) or at 470 K. At both temperatures the structural arrangements are very similar and produce a covalently bonded network. However, higher substrate temperatures produce a clearer structure due to the improved removal of impurities and/or water molecules that are produced during the polymerization.
  • the resulting network can be observed using a Scanning Tunneling Microscope or STM.
  • the organized structure is visually analyzed and found to be an ordered hexagonal structure of a 15.3 A pore size as can be seen in Fig. 6a and Fig. 6b.
  • This pore size corresponds closely to the pore size in the model from density functional theory (DFT) calculation of 15.25 A, as can be seen in Fig 7.
  • DFT density functional theory
  • the conditions for forming the network under UHV may depend on the reactants and the reactions that take place, but may be varied according to a sublimation temperature between ambient (-298K) and 500K, a pressure of approximately 1x10 7 - IxIO "8 Pascal, and a substrate temperature between 77K and 570K. However, these temperatures in no way restrict the range of reaction conditions and are provided here as a guide to the temperature and pressure ranges used.
  • the UHV applied to the samples after sublimation evaporates and evacuates the water generated during reaction; however the removal of this water can be accelerated by heating of the substrate either during the deposition or by post-deposition annealing.
  • the covalent nature of the network and the formed structural arrangements were found to be effectively independent of both the evaporator and substrate temperatures. However, it should be noted that higher substrate temperatures produce a clearer network due to the removal of some impurities and/or water molecules that are produced during the polymerization.
  • the extent of surface coverage can be varied between ⁇ 0.01 monolayer to >1 monolayer by control of the sublimation temperature and the sublimation time.
  • the formation process is self-limiting, so that the formation of a single monolayer is favored.
  • the formed networks show the same level of order and pore size, which indicates that there is not a surface area coverage effect on the network formation.
  • Image analysis techniques show that the majority of the pores are of a hexagonal structure, with secondary maxima corresponding to pentagon, heptagon, and octagon structures.
  • the hexagon structure is the most stable and lowest energy system and thus is, as expected, the dominant geometry in the network.
  • the different polygon structures are caused either by deformation of the perfect hexagon structure or by incomplete ring closure in the boroxine.
  • the network can be annealed after deposition at elevated temperatures (for example 475K) to eliminate impurities and the water produced during the network formation.
  • This annealing step may additionally help to complete any unfinished chemical reactions on the surface.
  • annealing seems ineffective with a covalent ordered organic network to remove defects, contrary to supramolecular networks, since the permanence of the covalent bond structures do not allow rearrangement.
  • the network comprising boroxine linkages is reversible in the presence of water under atmospheric conditions because the water molecules hydrolyze the chemical bonds.
  • the reaction and chemical bonds are permanent under conditions that are dry, UHV 1 and/or high temperature.
  • the thermal stability of the network was observed to confirm the covalent bonding of molecules. It was found that the materials are stable up to at least 725K for short periods of time (such as up to five minutes). This confirms the covalent nature of the network as weaker bonding structures are expected to degrade at lower temperatures. For longer periods of time (such as up to 15 hours) of heating, the structure remains intact at 625K but some degradation of the order in the network was noted for those at 725K.
  • boronic acids may also be reacted with themselves to obtain a boroxine ordered network.
  • Triboronic acids, tetraboronic acids, etc. may also be reacted with themselves to obtain a boroxine ordered network.
  • Fig. 2 shows an example of a covalent ordered organic network formed from the above-described trifunctional phenyltriboronic acid, by reacting the acid with itself.
  • Second embodiment formation of a monolayer network using two different reactants
  • a covalently linked, ordered monolayer network can also be formed by reacting a polyfunctional boronic acid with a second reactant.
  • the second reactant may comprise a polyfunctional diol forming a network linked through a dioxaborole.
  • the second reactant may comprise a polyfunctional diamine for producing a porous network linked through diazaboroles.
  • the second reactant may comprise of a polyfunctional amino alcohol to produce a network linked through oxazaboroles.
  • the second reactant may comprise of a polyfunctional thiol to produce a dithioborolane.
  • the second reactant may be a different polyfunctional boronic acid producing a network constructed using boroxine linkages (boronanhydrides). For instance, an "n1 -boronic" acid may be reacted with an "n2-boronic" acid, with "n1" different from “n2" and wherein "n” can be “di", "tri", “tetra”, etc.
  • the characteristics and properties of the resulting network may thereby be varied and altered by changing the reactants and by incorporating functional groups into the reactants. This allows for customization of the physical properties of the pores and/or the chemical properties of the monolayer.
  • a boronate-linked network is produced by a condensation reaction wherein BDBA (1 ,4-benzenediboronic acid) as first reactant is reacted with 2,3,6,7,10,11-hexahydroxytetrephenylene or HHTP (a polyfunctional alcohol) as second reactant, to obtain, as described below and also shown in Fig. 3, a self-assembled, ordered, stable, monolayer network:
  • Such a network is based on an esterification reaction between the boronic acid and the diol groups in the HHTP, to form boronate ester linkages.
  • the molecular network is for instance formed by the sublimation of BDBA and HHTP under UHV onto a flat surface, for instance a clean Ag (111 ) substrate using the methods described above, i.e. by sublimation under UHV.
  • the second reactant is deposited onto the surface in excess prior to the first reactant in order to prevent the BDBA from reacting with itself and therefore to inhibit the formation of the boroxine-linked network described above.
  • the BDBA is firstly purified by careful vacuum sublimation at 445K and 10 Pascal.
  • the BDBA and HHTP are then loaded into the sublimation equipment, and then out-gassed in vacuum and then evaporated from separate heated molybdenum crucible evaporators under ultra-high vacuum conditions (1x10 7 Pascal) onto the clean Ag surface.
  • the deposition rate is approximately 0.5 monolayer per minute (where one monolayer corresponds to the amount of material required to completely cover the surface with a single molecular layer of material).
  • HHTP molecules are then sublimed at an evaporation temperature of 500K.
  • the BDBA evaporator temperature can be varied between 370 and 460 K.
  • an entire monolayer is first deposited on the Ag(111 ) substrate at a sublimation temperature of 500 K and a substrate temperature of 298K, then both molecules are co- evaporated onto the sample at 400K.
  • the bi-molecular reaction of the boronate-linked network is preferred to the reaction of the boroxine-linked network.
  • the substrate is annealed at about 520K to remove excess HHTP molecules and water molecules produced during reaction.
  • the network obtained shows an average pore size of 29.9 A, as can be seen in Fig. 8a and Fig. 8b.
  • a pore size can be calculated from the analysis of STM images. This coincides well with the 29.8 A pore size derived from the calculation of a DFT model, as can be seen in Fig 9.
  • the network is dominated by hexagonal structures, which is the most energetically favorable structure.
  • the thermal stability of the network was observed to confirm the covalent bonding of molecules. It was found that the materials are stable up to at least 725K for short periods of time (such as up to five minutes). This confirms the covalent nature of the network as weaker bonding structures are expected to degrade at lower temperatures. For longer periods of time (such as up to 15 hours) of heating, the structure remains intact at 625K but some degradation of the order in the network was noted for those at 725K.
  • the first reactant may comprise a boronate ester instead of a polyfunctional boronic acid.
  • the boronate ester may be reacted with a second reactant such as a polyfunctional diol, a polyfunctional diamine, a polyfunctional amino alcohol, or a polyfunctional thiol in an exchange type reaction to from a more stable dioxaborole, diazaborole, oxazaboroles or dithioborolane.
  • Such an embodiment may be useful because boronic esters behave like the acids whilst they do not form boroxines (they do not react with themselves) and they may be more volatile and thus easier to sublime.
  • the formation of a bimolecular boronate network is achieved by the reaction of an alkyl boronic ester with a polyfunctional aromatic alcohol.
  • the formation reaction in this case is driven by a transesterification reaction between a boronic ester with a polyfunctional alcohol that forms a more stable boronic ester.
  • This could be a reaction of for example an alkyl diester of 1 ,4-benzenediboronic acid reacting with for example 2,3,6,7,10,11-hexahydroxy-triphenylene to form the same network as shown in Fig. 1.
  • boronic esters is firstly achieved by the heating of a boronic acid with an alkyl alcohol or an alkyl diol under simple lab conditions. One of these esters is then deposited with an aryl polyfunctional alcohol. An exchange reaction takes place, which displaces the alkyl diol or alkyl alcohols and replaces it with the aromatic polyfunctional alcohol as described below:
  • R is an alkyl or aryl group
  • a boronate-linked network can then be formed as can be seen in Fig. 5.
  • the boroxine- and boronate- linked networks that have been disclosed above display thermal stability until at least 725K at which point some degradation and delamination of the network is noted. This degradation temperature was confirmed by Thermogravimetric Analysis or TGA.
  • these networks offer significantly improved order and ease of reaction. Furthermore, compared with non-covalent systems, they offer significantly improved stability in relation to thermal stability and atmospheric pressures, as well as resistance during further reaction.
  • reactants can be varied to adjust the pore-size, functionality, properties and characteristics in the desired final product, yet the acid/ester equilibrium and anhydride bonds retain reversible characteristics of a self-assembling system including self-repair and efficient formation.
  • Other combinations of reactants can be varied to adjust the pore-size, functionality, properties and characteristics in the desired final product, yet the acid/ester equilibrium and anhydride bonds retain reversible characteristics of a self-assembling system including self-repair and efficient formation.
  • the above disclosed process for synthesizing an ordered monolayer porous covalently- linked organic network is susceptible of various other embodiments.
  • the reactants can be initially deposited and then the network formation is driven by application of a reduced pressure, in the range of 10 3 to 10 "6 Pascal, and/or an elevated temperature in the range of 375-775K.
  • a reduced pressure in the range of 10 3 to 10 "6 Pascal
  • an elevated temperature in the range of 375-775K.
  • any drying conditions will cause the network to form, including dry atmosphere and dry solvents. The speed of the reaction will depend upon the conditions.
  • Functionalized reactants may then be reacted with a boronic acid or boronic ester as described in the earlier embodiments.
  • a functionality may be added to the 3, 6 position of 1 , 2, 4, 5-tetrahydroxy benzene, as can be seen below.
  • the functionality may comprise, for instance, of alkyl, trimethyl silyl (TMS) or carbonic acid functionalities.
  • this functionalized reactant is reacted with boronic acid to form a boronic ester linked network.
  • the characteristics and properties (such as the pore-size, functionality, properties, and characteristics) of the resulting network may be varied and altered in a predictable manner by adjusting the reactants and by incorporating functional groups into the reactants before formation.
  • the networks can be tailored -i.e. customized- to fit specific requirements and desired properties, for example by using the complexing ability of amines on the size of the pores.
  • functionality may also be incorporated by including heterocyclic macrocycles, such as phthalocyanines or porphyrins, into the structure either by using a diol or diamine functionalized macrocycle or a boronic acid macrocycle.
  • heterocyclic macrocycles such as phthalocyanines or porphyrins
  • covalently linked, ordered monolayer networks may also be formed from boronate- or boroxine-based systems on a molecularly flat surface by various methods other than sublimation. Such methods of formation may include physisorption of reactants from solution, precipitation polymerization, spin coating, or any combination of these techniques.
  • An ordered monolayer porous covalently-linked organic network made according to one embodiment of the invention is susceptible of various applications.
  • the network is used as a mask to deposit an ordered array of metal particles such as cobalt, iron, platinum and zinc or metallic alloys or other functional materials such as Fullerene molecules for nano-electronics applications.
  • metal particles such as cobalt, iron, platinum and zinc or metallic alloys or other functional materials such as Fullerene molecules for nano-electronics applications.
  • the capability of the network to trap molecules can be shown by the deposition of a material (such as cobalt or Fullerene molecules) into the pores of the network for devices such as nano-scale hard drives or Random Access Memory (RAM).
  • a material such as cobalt or Fullerene molecules
  • RAM Random Access Memory
  • bio molecules or bio-receptors may be placed in the pores to produce nano-biological networks.
  • the network has application in the modification of the electronic, chemical and physical properties of surfaces using such organized two-dimensional molecular networks.
  • the network can be readily hydrolyzed in a humid atmosphere in order to remove the network after its utilization if required.
  • Other conventional removal methods may be used by those skilled in the art, as chemical etching, plasma etching, etc.

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Abstract

L’invention concerne un procédé pour la synthèse d’un réseau ordonné covalent sur une surface, comprenant le dépôt sur ladite surface d’un acide boronique polyfonctionnel ou d’un ester de boronate et la réaction de l’acide boronique polyfonctionnel ou de l’ester de boronate avec un second réactif de façon à obtenir un réseau monocouche organique lié par une boroxine ou lié par un boronate. L'invention concerne également une monocouche ordonnée covalente sur une surface, comprenant un réseau lié par une boroxine ou lié par un boronate et ayant une structure bidimensionnelle poreuse à l’échelle nanométrique. Le réseau lié par une boroxine ou lié par un boronate peut avoir une prédominance de pores structurés.
PCT/IB2008/002342 2008-04-18 2008-04-18 Synthèse d’un réseau monocouche covalent ordonnée sur une surface WO2009127896A1 (fr)

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