Cycloalkyl norbornene compounds with heterocyclic functional groups for rapid, low temperature, low VOC surface functionalization

Abstract

The invention discloses a series of norbornene compounds with heterocyclic functional groups and a preparation method of the norbornene compounds. Fast, low temperature, low VOC methods of attaching these norbornene compounds to a surface to serve as chemical attachment points for various functionalized molecules are also described.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 429,193, filed on December 1, 2022, the entire content of which is incorporated herein by reference. Background of the Invention

[0003] Norbornene units have long been used to confer excellent properties on polymer systems due to their rigid structure, which results in a high glass transition temperature that is crucial in many applications. In addition, norbornene units have a highly specific reactivity, different from chemically similar compounds such as vinyl or allyl, and have been used, for example, to attach reactive polymers to glass or polymer substrates for biomolecule detection, proteomics, and nucleic acid sequencing. The ability to readily attach norbornene - containing compounds to surfaces via a fast, low - temperature, low - VOC process would reduce environmental impact, material consumption, and capital costs, while enabling the ability to provide norbornene functional groups on substrates with limited temperature stability. Summary of the Invention

[0004] In one embodiment, aspects of the present invention disclose a norbornene compound having Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), or Formula (VI):

[0005]

[0006] wherein p is 0, 1, or 2; Q1 and Q2 are independently O, S, N(R 13 ), C = O, C(R 14 )(R 15 ), or (R 14 )(R 15 )C - C-(R 16 )(R 17 ); J1 and J2 are independently O, S, N(R 18 ), C = O, or C(R 19 )(R 20 ); J3 is N or C(R 19 );

[0007] R 11 is a (C5 - C12) aliphatic group, (C5 - C12) heterocyclic group, or (C6 - C14) aromatic group bonded to both J1 and J2, or has Formula [T]:

[0008]

[0009] wherein T1, T2, T3, and T4 are each independently selected from the group consisting of: O, S, N(R21 ), C═O and C(R 22 )(R 23 ), where each of S1, S2, S3 and S4 is 0 or 1, provided that S1 + S2 + S3 + S4 > 0; wherein if S1 + S2 + S3 + S4 ≥ 2, then [T] is a bidentate ligand bonded to both J1 and J2;

[0010] R 12 is a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both J3 and J2, or has the formula [U]:

[0011]

[0012] wherein U1 is N or C(R 22 ); U2, U3 and U4 are each independently selected from the group consisting of: O, S, N(R 21 ), C═O and C(R 22 )(R 23 ), where each of S5, S6 and S7 is 0 or 1; wherein if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bonded to both J1 and J3;

[0013] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are the same or different and are each independently selected from the group consisting of: a single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, linear or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6) acyl, (C2-C8) acyloxy, (C6-C14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14 ) aryl(C1-C6)alkoxy, (C1-C 12 ) alkyl(C1-C 12 ) perfluoro group, and at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 is substituted with a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H):

[0014]

[0015]

[0016] wherein Z is a Group 14 element other than carbon; X is a Group 15 element; Y is a Group 16 element; m and n are each independently an integer from 1 to 10; K1 and K2 are independently O, S, N(R 34 ), or C(R 35 )(R 36 ); R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group bonded to both J1 and J2, or has formula [W]:

[0017]

[0018] wherein W1, W2, W3 and W4 are each independently selected from the group consisting of: O, S, N(R 37 ), C═O and C(R 39 )(R 39 ), each S8, S9, S 10 and S 11 is 0 or 1, provided that S8 + S9 + S 10 + S 11> 0; wherein if S8 + S9 + S 10 + S 11 ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2;

[0019] R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 34 、R 35 、R 36 、R 37 、R 38 and R 39 are the same or different and each independently is a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, linear or branched (C3 - C 18 ) alkyl, (C2 - C 18 ) alkenyl, (C3 - C 18 ) alkoxy, tris(C1 - C6)alkylsilyl, tris(C1 - C6)alkoxysilyl, di(C1 - C6)alkylamino, di(C1 - C6)alkyl(C1 - C6)alkylamino, perfluoro(C1 - C 18 ) alkyl, (C3 - C 12 ) cycloalkyl, (C6 - C 12 ) bicyclo(C1 - C6)alkyl, (C7 - C 14 ) tricyclo(C1 - C6)alkyl, (C1 - C 18 ) thioalkyl, (C2 - C6)acyl, (C2 - C8)acyloxy, (C6 - C 14 ) aryl, (C6 - C 14 ) aryl(C1 - C8)alkyl, perfluoro(C6 - C 14 ) aryl, perfluoro(C6 - C 14 ) aryl(C1 - C3)alkyl, (C6 - C 14 ) aryloxy, (C6 - C 14 ) aryl(C1 - C6)alkoxy or (C1 - C 12 ) alkyl(C1 - C 12 ) perfluoro group; wherein R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R34 , R 35 , R 36 , R 37 , R 38 and R 39 At least one of them is a single bond connecting to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

[0020] Advantageous improvements of the present invention, which can be implemented alone or in combination, are specified in the dependent claims.

[0021] In summary, the following particularly preferred embodiments are proposed within the scope of the present invention:

[0022] Embodiment 1: A norbornene compound having formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI):

[0023]

[0024] wherein p is 0, 1 or 2; Q1 and Q2 are independently O, S, N(R 13 ), C=O, C(R 14 )(R 15 ) or (R 14 )(R 15 )C-C-(R 16 )(R 17 ); J1 and J2 are independently O, S, N(R 18 ), C=O or C(R 19 )(R 20 ); J3 is N or C(R 19 );

[0025] R 11 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group or a (C6-C14) aromatic group bonded to both J1 and J2, or has formula [T]:

[0026]

[0027] wherein T1, T2, T3 and T4 are each independently selected from the group consisting of: O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), each of S1, S2, S3 and S4 is 0 or 1, provided that S1 + S2 + S3 + S4 > 0; wherein if S1 + S2 + S3 + S4 ≥ 2, then [T] is a bidentate ligand bonded to both J1 and J2;

[0028] R 12(C5-C12) aliphatic group or (C5-C12) heterocyclic group bonded to both J3 and J2, or having formula [U]:

[0029]

[0030] wherein U1 is N or C(R 22 ); U2, U3 and U4 are each independently selected from the group consisting of: O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), each of S5, S6 and S7 is 0 or 1; wherein if S5+S6+S7≥1, then [U] is a bidentate ligand bonded to both J1 and J3;

[0031] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are the same or different and are each independently selected from the group consisting of: single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6) acyl, (C2-C8) acyloxy, (C6-C 14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14)Aryl(C1-C6)alkoxy, (C1-C 12 )alkyl(C1-C 12 )a perfluoro group, and at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 is substituted by a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H):

[0032]

[0033] wherein Z is a Group 14 element other than carbon; X is a Group 15 element; Y is a Group 16 element; m and n are each independently an integer from 1 to 10; K1 and K2 are independently O, S, N(R 34 ), or C(R 35 )(R 36 ); R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group bonded to both J1 and J2, or has formula [W]:

[0034]

[0035] wherein W1, W2, W3 and W4 are each independently selected from the group consisting of: O, S, N(R 37 ), C=O and C(R 39 )(R 39 ), each S8, S9, S 10 and S 11 is 0 or 1, provided that S8 + S9 + S 10 + S 11 > 0; wherein if S8 + S9 + S 10 + S 11 ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2;

[0036] R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 are the same or different and each independently is a single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, linear or branched (C3-C 18 )alkyl, (C2-C 18 )alkenyl, (C3-C 18 )alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 )bicyclo(C1-C6)alkyl, (C7-C 14 )tricyclo(C1-C6)alkyl, (C1-C 18 )thioalkyl, (C2-C6)acyl, (C2-C8)acyloxy, (C6-C 14 )aryl, (C6-C 14 )aryl(C1-C8)alkyl, perfluoro(C6-C 14 )aryl, perfluoro(C6-C 14 )aryl(C1-C3)alkyl, (C6-C 14 )aryloxy, (C6-C 14 )aryl(C1-C6)alkoxy or (C1-C 12 )alkyl(C1-C 12 )perfluoro group; wherein at least one of R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 is a single bond connected to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

[0037] Embodiment 2: The norbornene compound as described in Embodiment 1, wherein Z is silicon or germanium.

[0038] Embodiment 3: The norbornene compound as described in Embodiment 1 or 2, wherein X is nitrogen.

[0039] Embodiment 4: The norbornene compound as described in any one of Embodiments 1 to 3, wherein Y is sulfur, selenium or tellurium.

[0040] Embodiment 5: The norbornene compound as described in any one of Embodiments 1 to 4, wherein p = 0, m = 1 and n = 1.

[0041] Embodiment 6: The norbornene compound as described in any one of Embodiments 1 to 5, wherein R 24 is a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl or tert-butyl, R 25 and R 26 are a single bond, hydrogen, methyl, methoxy or ethoxy, R 27 、R 28 、R 29 、R 30 、R 31 and R 32 are independently a single bond, hydrogen or methyl, Z is silicon, X is nitrogen or Y is sulfur.

[0042] Embodiment 7: The norbornene compound as described in any one of Embodiments 1 to 6, wherein the compound is N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane or N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-diethoxysilacyclopentane.

[0043]

[0044] Embodiment 8: The norbornene compound as described in any one of Embodiments 1 to 7, having a structure selected from the following group:

[0045]

[0046] Embodiment 9: A method for preparing a norbornene-functionalized surface, comprising: exposing a substrate containing hydroxyl surface groups to the norbornene compound as described in any one of Embodiments 1 to 8.

[0047] Embodiment 10: The method as described in Embodiment 9, comprising: exposing the norbornene compound in the gas phase to the substrate.

[0048] Embodiment 11: The method according to Embodiment 10, wherein the gas-phase exposure is carried out at a temperature below about 80 °C.

[0049] Embodiment 12: The method according to Embodiment 11, wherein the gas-phase exposure is carried out at a temperature below about 50 °C.

[0050] Embodiment 13: The method according to Embodiment 12, wherein the gas-phase exposure is carried out at a temperature below about 30 °C.

[0051] Embodiment 14: The method according to Embodiment 9, comprising: liquid-phase exposing the norbornene compound to the substrate.

[0052] Embodiment 15: The method according to Embodiment 14, wherein the liquid-phase exposure comprises spin coating, dip coating, coating on the substrate by wiping a liquid, or spraying.

[0053] Embodiment 16: A method of preparing a reactive polymer layer bonded to a substrate, the method comprising: coating a norbornene-functionalized surface as described in Embodiment 9 with a polymer comprising norbornene-reactive functional groups.

[0054] Embodiment 17: The method according to Embodiment 16, wherein the polymer comprising norbornene-reactive functional groups comprises azide, thiol, or tetrazine functional groups.

[0055] Embodiment 18: The method according to Embodiment 16, wherein the polymer comprising norbornene-reactive functional groups is coated on the norbornene-functionalized surface by spin coating, dip coating, coating on the substrate by wiping a liquid, or spraying. Detailed Description

[0056] Aspects of the present disclosure relate to a series of norbornene compounds having heterocyclic functional groups, and a rapid, volatile organic compound (VOC)-free or VOC-reduced method of attaching these norbornene compounds to a surface. In certain embodiments, the present invention relates to a series of cyclic azidosilane and thiidosilane compounds that, through norbornene functional groups or heterocyclic functional groups, serve as rapid, VOC-free or VOC-reduced selective surface functionalizing agents.

[0057] Unless otherwise indicated, any numerical values recited in this invention are to be understood as being modified in all instances by the term "about". Thus, the numerical values generally include the value recited plus or minus 10% thereof. For example, a temperature of "10 °C" or "about 10 °C" includes 9 °C and 11 °C and all temperatures in between. Additionally, unless the context clearly dictates otherwise, all numerical ranges recited in the specification are expressly inclusive of all possible sub-ranges, all individual numerical values within that range, including integers within that range, as well as fractions and decimals of the numerical values. All ranges of carbon chain lengths are to be understood as including all carbon chain lengths within that range. For example, "(C3-C18) alkyl, straight or branched" is to be understood as including all straight and branched alkyl groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms.

[0058] Norbornene compound

[0059] As described in more detail below, aspects of the present invention relate to norbornene compounds containing a heterocyclic group, which may be suitable for the preparation of surfaces containing norbornene functional groups. Norbornene is a highly strained bridged cycloalkane composed of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The simplest norbornene compound, bicyclo[2.2.1]hept-2-ene, has the following structure (showing two different depictions of the same molecule):

[0060]

[0061] More generally, the present invention relates to norbornene compounds having formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI):

[0062]

[0063] In formulas (I), (II), (III), (IV), (V), and (VI), p is 0, 1, or 2; Q1 and Q2 are independently O, S, N(R 13 ), C=O, C(R 14 )(R 15 ) or (R 14 )(R 15 )C-C-(R 16 )(R 17 ); J1 and J2 are independently O, S, N(R 18 ), C=O or C(R 19 )(R 20 ); J3 is N or C(R 19 );

[0064] R 11(C5-C12) aliphatic group, (C5-C12) heterocyclic group or (C6-C14) aromatic group bonded to both J1 and J2, or having formula [T]:

[0065]

[0066] wherein T1, T2, T3 and T4 are each independently selected from the group: O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), each S1, S2, S3 and S4 is 0 or 1, provided that S1 + S2 + S3 + S4 > 0; wherein if S1 + S2 + S3 + S4 ≥ 2, then [T] is a bidentate ligand bonded to both J1 and J2;

[0067] R 12 is a (C5-C12) aliphatic group or (C5-C12) heterocyclic group bonded to both J3 and J2, or having formula [U]:

[0068]

[0069] wherein U1 is N or C(R 22 ); U2, U3 and U4 are each independently selected from the group: O, S, N(R 21 ), C=O and C(R 22 )(R 23 ); each S5, S6 and S7 is 0 or 1; wherein if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bonded to both J1 and J3;

[0070] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are the same or different and are each independently selected from the group: single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, linear or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18)alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 )bicyclo(C1-C6)alkyl, (C7-C 14 )tricyclo(C1-C6)alkyl, (C1-C 18 )thioalkyl, (C2-C6)acyl, (C2-C8)acyloxy, (C6-C 14 )aryl, (C6-C 14 )aryl(C1-C8)alkyl, perfluoro(C6-C 14 )aryl, perfluoro(C6-C 14 )aryl(C1-C3)alkyl, (C6-C 14 )aryloxy, (C6-C 14 )aryl(C1-C6)alkoxy, (C1-C 12 )alkyl(C1-C 12 )perfluoro, and at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 is substituted with a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), or formula (H):

[0071]

[0072] Z is a Group 14 element other than carbon; X is a Group 15 element; Y is a Group 16 element; m and n are each independently an integer from 1 to 10; K1 and K2 are independently O, S, N(R 34 ), or C(R 35 )(R 36 ); R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group bonded to both J1 and J2, or has formula [W]:

[0073]

[0074] Among them, W1, W2, W3, and W4 are each independently selected from the following group: O, S, N(R 37 ), C═O, and C(R 38 )(R 39 ), S8, S9, S 10 and S 11 are each 0 or 1, provided that S8 + S9 + S 10 + S 11 > 0; wherein if S8 + S9 + S 10 + S 11 ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2;

[0075] R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 are the same or different and are each independently a single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, straight-chain or branched-chain (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6) acyl, (C2-C8) acyloxy, (C6-C 14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14)Aryl(C1-C6)alkoxy or (C1-C 12 )Alkyl(C1-C 12 )Perfluoro; where R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 34 、R 35 、R 36 、R 37 、R 38 and R 39 in which at least one is a single bond connecting to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

[0076] In formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI), Q1 and Q2 form a bridge of a norbornene structure, preferably, but not limited to, CH2, C(CH3)2, O, N(CH3) and CH2-CH2; p is 0, 1 or 2; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 and R 23 independently, preferably, without limitation, are single bond, hydrogen, methyl, vinyl, ethyl, n-propyl or n-butyl, provided that at least one of R1, R2, R3, R4, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 must contain or be substituted by a heterocyclic group of formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H); preferably, J1 and J2 are independently NH, N(CH3), O or CH2, preferably, J3 is N, CH or C(CH3).

[0077] In the most preferred embodiment, the norbornene compound has the formula (I), Q1 is CH2, p = 0, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 is hydrogen, provided that one of R1, R2, R3, and R4 is not hydrogen and is substituted with a heterocyclic group of formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), or formula (H).

[0078] In formulas (A), (B), (C), (D), (E), (F), (G), and (H), Z is a Group 14 element other than carbon, e.g., without limitation, silicon or germanium; X is a Group 15 element, e.g., without limitation, nitrogen or phosphorus; Y is a Group 16 element, e.g., without limitation, sulfur, selenium, or tellurium. Thus, each of the functional groups (A) through (H) contains a bond between a Group 14 element (Z) and a Group 15 element (X) or a Group 16 element (Y).

[0079] In formulas (A), (B), (C), (D), (E), (F), (G), and (H), R 24 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 , and R 39 are independently, without limitation, preferably a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl, or tert-butyl, and R 25 and R 26 are independently preferably a single bond, hydrogen, methyl, ethyl, methoxy, or ethoxy, provided that R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 , and R 39At least one of them must be a single bond connected to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

[0080] In a preferred embodiment, the structure of the heterocyclic component has formula (A) or formula (B), m = 1 or 2, n = 1 or 2, R 24 , R 27 , R 28 and R 29 are independently a single bond, hydrogen or methyl, R 25 and R 26 are a single bond, hydrogen, methyl, methoxy or ethoxy, Z is silicon, X is nitrogen and Y is sulfur.

[0081] In the most preferred embodiment, the structure of the heterocyclic component has formula (A), m = 1, n = 1, R 24 , R 27 , R 28 and R 29 are independently a single bond, hydrogen or methyl, R 25 and R 26 are a single bond, methyl, methoxy or ethoxy, Z is silicon and X is nitrogen.

[0082] For compounds having formula (E), formula (F), formula (G) and formula (H), a bridging structure is formed by groups K1, K2 and R 33 , R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group or a (C6-C14) aromatic group bonded to both K1 and K2, or has formula [W] as defined above:

[0083]

[0084] Preferably, K1 and K2 are independently selected from NH, N(CH3), O or CH2.

[0085] In a preferred compound containing formula (E), formula (F), formula (G) and formula (H), K1 and K2 are O, S8 and S9 = 1, S 10 and S 11 = 0, and W1 and W2 are CH2, CH(CH3) or C(CH3)2.

[0086] The difference between the norbornene compounds having formula (I) and (II) is that the former has four independent ligands R1, R2, R3 and R4 (usually two or three of which are hydrogen), while the latter contains a cyclic substituent (J1-R 11 -J2) that consumes two ligand positions. The difference between formula (II) and formula (III) is that J3 and R 12The adjacent atoms in it have a double bond, while the adjacent atoms of J2 and R 11 have a single bond.

[0087] Similarly, the difference between the norbornene compounds of formulas (IV) and (V) is that the former has two independent ligands R2 and R3, while the latter contains a cyclic substituent (J1-R 11 -J2) that consumes two ligand positions. The difference between formulas (V) and (VI) is that J3 and R 12 The adjacent atoms in it have a double bond, while the adjacent atoms of J2 and R 11 have a single bond.

[0088] The difference between formulas (I), (II), and (III) and formulas (IV), (V), and (VI) is the presence of double bonds in place of the independent substituents R1 and R4.

[0089] Exemplary compounds of formula (I) are shown as formulas (VII) and (VIII) below at p = 0 and p = 1, respectively. For the compound of formula (VII), the variables in formula (I) are as follows: p = 0, Q1 = C(R 14 )(R 15 ), R 14 =R 15 =H, m = n = 1, R 25 =R 26 =CH3, R 27 =R 28 =R 29 =H, Z = Si, X = N, R2, R3, R4, R7, R8, R9, and R 10 =H, R1 is a methyl group substituted by a compound of formula (A), and R 24 is a single bond connecting the heterocyclic group to the norbornene moiety of formula (I). For the compound of formula (VIII), the variables in formula (I) are as follows: p = 1, Q1 = Q2 = C(R 14 )(R 15 ), R 14 =R 15 =H, m = n = 1, R 25 =R 26 =CH3, R 27 =R 28 =R 29 =H, Z = Si, X = N, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 =H, R1 is a methyl group substituted by a compound of formula (A), and R 24 is a single bond connecting the heterocyclic group to the norbornene moiety of formula (I).

[0090]

[0091] Among them, exemplary compounds of formula (II) or formula (III) containing carbon, nitrogen and oxygen, J1, J2 and J3 are shown by the following formulas (IX), (X) and (XI) respectively.

[0092]

[0093] For the compound of formula (IX), the variables in compound (II) are as follows: p = 0, Q1 = C(R 14 )(R 15 ), R 14 = R 15 = H, J1 = CH(R 20 ), R 20 is a single bond connecting to the heterocycle of formula A, J2 = CH2, R 11 = CH2 (S1 = 1, S2 = S3 = S4 = 0, T1 = CH2), m = n = 1, Z = Si, X = N, R 25 = R 26 = CH3; R1, R4, R7, R8, R9, R 10 , R 14 , R 28 and R 29 = H, R 27 = a single bond connecting to the compound of formula (II). In formula (X), p = 0, Q1 = C(R 14 )(R 15 ), R 14 = R 15 = H, J1 = N(R 18 ), R 18 is a single bond connecting to the heterocycle of formula A, R 12 = N (S5 = S6 = S7 = 0, U1 = N), R 25 = R 26 = CH3; R1, R4, R7, R8, R9, R 10 , R 24 , R 28 and R 29 = H, R 27 = a single bond connecting to the compound of formula (III). In formula (XI), p = 0, Q1 = C(R 14 )(R 15 ), R 14 = R 15 = H, J1 = J2 = O, R5 = CH(R 23 )(S1 = 1, S2 = S3 = S4 = 0, T1 = CH(R 23 ))), R 23= a single bond connecting to a heterocycle of formula A, R 25 = R 26 = CH3; R1, R4, R7, R8, R9, R 10 , R 24 , R 28 and R 29 = H, R 27 = a single bond connecting to a compound of formula (II).

[0094] Considering the heterocyclic moiety of the norbornene compound, there are three key variables in the core structure, resulting in eight possible functional groups of formulas (A) through (H).

[0095] The first variable is the simple ring structure versus the "silatrane" structure, which group contains a nitrogen atom in the chain that can form a weak bond with the Z atom (usually Si) and form a pseudo-bicyclic structure in formulas (C), (D), (G), and (H). Functional groups (A), (B), (E), and (F) contain simple ring groups.

[0096] Exemplary norbornene compounds containing a simple ring group (formula (A)) and a silatrane group (formula (C)) are shown by the following formulas (XII) and (XIII):

[0097]

[0098] The second variable concerns the Z position (usually Si), which contains two bonds not belonging to the ring. These can be independent ligands such as alkoxy or alkyl groups, or a bidentate bridging structure that consumes two sites, as shown in groups (E) through (H).

[0099] An exemplary norbornene compound having a bidentate bridging ligand and containing functional group (E) has formula (XIV). In formula (E), K1 and K2 are oxygen, and R 33 is a (C6) aryl group bonded to both K1 and K2:[[]]END]]

[0100]

[0101] The third variable concerns the X / Y position (usually N or S), which differs in that there is a third bond (R 14 ) in the case of N, while there is no third bond in the case of S or other Group 16 elements. These differences are described in formulas (A) versus (B), (C) versus (D), etc. For example, the following compound (XV) contains an X substituent (here nitrogen), while the following compound (XVI) contains a Y substituent (here sulfur).

[0102]

[0103] The compounds disclosed by the present invention contain a norbornene fragment, as described by formula (I), formula (II), formula (III), formula (IV), formula (V), formula (VI), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 and R 23 at least one of which contains or is substituted by a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H). It should be understood that "comprises" means that the heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H) is directly singly bonded to the norbornene fragment described by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI), and the positions of R1, R2, R3, R4, R6, R7, R8, R9, R 10 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 21 、R 22 and R 23 that are directly bonded to the norbornene fragment are the same as the R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 34 、R 35 、R 36 、R 37 、R 38 and R 39 of the heterocyclic group. In this case, the norbornene group and the heterocyclic group can be considered to be directly bonded.

[0104] Among R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 、R13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 When it contains a heterocyclic group having the formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H), the connecting positions R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 or R 23 Consisting of methyl, ethyl, methoxy, ethoxy, straight-chain or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6)acyl, (C2-C8)acyloxy, (C6-C 14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14 ) aryl(C1-C6)alkoxy, (C1-C 12 ) alkyl(C1-C 12 ) perfluoro, where at any chemically suitable position of the R group, the R group and the R of the heterocyclic group 24 , R 25, R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 and R 39 There is a single bond between the positions. In this case, the norbornene compound and the heterocyclic group can be considered to be bonded through a bridging group containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 or R 23 .

[0105] The following formulas (XVII), (XVIII), (XIX) and (XX) show the difference between directly bonded norbornene and heterocyclic groups and those bonded through a bridging group. In the directly bonded formula (XVII), there is a single bond between the R4 position of the norbornene group in formula (I) and the R 24 position on the nitrogen atom of the heterocyclic group in formula (A), while in the directly bonded formula (XVIII), there is a single bond between the R 14 position of the norbornene group in formula (I) and the R 25 position on the silicon atom of the heterocyclic group in formula (A).

[0106] In formulas (XIX) and (XX), examples of bonding through a bridging group are shown. In the bridge-bonded formula (XIX), there is a methyl group substituted by the heterocyclic group in formula (A) at the R1 position of the norbornene group, and the methyl group is singly bonded to the R 24 position on the heterocyclic nitrogen atom. In the bridge-bonded formula (XX), there is a (C6) aryl (phenyl) group at the R4 position of the norbornene group, and the (C6) aryl group is substituted by the heterocyclic group in formula (A) at the meta position, and the (C6) aryl group is singly bonded to the R 27 position on the heterocyclic carbon atom.

[0107]

[0108] The compounds disclosed in the present invention may have more than one heterocyclic group of formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H), as shown in formula (XXI) below, or more than one norbornene group of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI), as shown in formula (XXII) below. In compounds having more than one heterocyclic group, they may be the same or different and are bonded to one or more norbornene groups at the positions defined above. Similarly, in compounds having more than one norbornene group, the norbornene groups may be the same or different and are bonded to one or more heterocyclic groups at the positions defined above.

[0109]

[0110] Representative examples of norbornene - heterocyclic compounds according to aspects disclosed in the present invention are shown below.

[0111]

[0112] Although the formulas and structures described herein do not show any stereochemical designations, unless otherwise stated, the norbornene compounds described herein comprise mixtures of diastereoisomers which generally retain their configuration when the double bonds are reacted in the following manner. As a representative example, the following figure shows the R and S enantiomers of the exo and endo isomers of a creative norbornene structure, which results from two different groups being attached to the C4 or C5 carbon of norbornene. Since these exo and endo isomers and their enantiomers may have different properties, it should be understood that taking advantage of these differences (e.g., using substantially pure exo or endo isomers, or R or S enantiomers, or mixtures enriched in either isomer or enantiomer) is within the scope of the disclosure of the present invention.

[0113]

[0114] Surface functionalization

[0115] More embodiments of the present invention relate to functionalizing a surface with norbornene groups in a fast, volatile organic compound (VOC) - free or low - VOC manner using a suitable heterocyclic group that undergoes a ring - opening reaction with the hydroxyl groups of the target substrate.

[0116] More specifically, aspects of the present invention relate to attaching the norbornene compounds described herein to: (a) a substrate comprising surface hydroxyl groups, such as glass, quartz, alumina, and titanium dioxide; (b) a polymeric substrate whose surface inherently has hydroxyl groups as part of its chemical structure, such as epoxy resins or polyurethanes; or (c) a substrate that has been treated to provide surface hydroxyl groups, such as silicone, polyester, polystyrene, butadiene rubber, polyethylene, or polypropylene, treated by an oxidation process such as ozone, ozone / ultraviolet light, plasma, or corona.

[0117] It is known in the art that norbornene groups can be attached to such substrates by using trialkoxysilyl-functionalized norbornenes (such as [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane). However, the reaction rate of such molecules is low, requiring approximately one hour and an elevated deposition temperature of about 100 °C to achieve sufficient coverage for most applications. In addition, a post-curing step at about 100 °C for about one hour is typically also required to further condense the remaining alkoxy groups to a final stable state. Moreover, exposure to these compounds typically results in physical adsorption of excess material on the substrate surface, which requires additional treatment to remove prior to the curing step. Additionally, the reaction chemistry of the deposition process involves the generation of volatile organic components (methanol in this case), which further raises process safety and environmental concerns.

[0118] However, it has been found that the norbornene heterocyclic compounds of the present invention (comprising norbornene chemically bonded to a heterocyclic compound, the bond being between a Group 14 element and a Group 15 or Group 16 element) will rapidly ring-open in the presence of hydroxyl groups and can be used to attach norbornene functional groups to hydroxyl-containing substrates without releasing VOCs.

[0119] It should be understood that no volatile organic compounds (VOCs), such as methanol or ethanol, are released when using the heterocyclic compounds of the present invention to react with a hydroxylated surface. If the heterocyclic compounds of the present invention do not contain alkoxy groups or other reactive groups, the use of the compounds in the process of the present invention will be VOC-free. However, if the molecules of the present invention do contain alkoxy groups or other reactive groups capable of undergoing secondary reactions, VOCs may be released upon their reaction or curing. In such cases, compared to the comparative process (which releases alcohols both during the initial reaction with the substrate and during subsequent reaction or curing), the process of the present invention is VOC-reduced.

[0120] Thus, in an aspect disclosed by the present invention, a method for preparing a norbornene-functionalized surface comprises: exposing a substrate comprising surface hydroxyl groups to the norbornene compounds described herein. The exposure can be a vapor-phase exposure carried out by any means known in the art, such as chemical vapor deposition (CVD), and is carried out by exposing the substrate to the vapor of the compounds of the present invention on a time scale of less than about one hour at a temperature below about 80 °C, or more preferably below about 50 °C, and most preferably below about 30 °C. Liquid-phase exposure (wherein the norbornene compound can optionally be dissolved in a non-hydrolytic solvent such as toluene, tetrahydrofuran or dimethoxyethane) can be carried out by spin coating, dip coating, wiping, spraying or other means known in the art.

[0121] Scheme 1 shows a hydroxylated surface functionalized with norbornene groups according to such a method.

[0122]

[0123] Use of Norbornene-Functionalized Surfaces as Coupling Agents

[0124] In another embodiment disclosed by the present invention, a surface coated with the compounds of the present invention can be used to bind molecules or polymers that are reactive towards norbornene groups. Such molecules or polymers known in the art can contain reactive groups such as azides, thiols or tetrazoles, which are known to react with norbornene groups in a rapid "click chemistry" manner. Norbornene groups can be used to directly link to a suitably functionalized target molecule, as shown in Scheme 2; or to a suitably functionalized binding layer that in turn binds a suitably functionalized target molecule, as shown in Scheme 3. Target molecules can include, but are not limited to, for example, molecules designed to detect, react with or bind to biomolecules such as nucleic acids, proteins, lipids or carbohydrates. Suitable binding layers can include, but are not limited to, polymers functionalized with multiple azide, thiol or tetrazole groups.

[0125]

[0126] In Schemes 2 and 3, "X" represents a norbornene-reactive group such as azide, thiol or tetrazole; and in Scheme 3, "Y" represents a group that is reactive towards a norbornene-reactive group such as norbornene or alkyne.

[0127]

[0128] Azide, thiol and tetrazole groups suitable for binding to norbornene-functionalized surfaces are shown below, where R represents an organic or organic / inorganic compound.

[0129]

[0130] The present invention will now be described in connection with the following non - limiting examples.

[0131] Example 1: Synthesis of N - [(bicyclo[2.2.1]hept - 2 - enyl)methyl]aza - 2,2 - dimethoxysilacyclopentane

[0132]

[0133] A 1 L four - necked flask was equipped with a magnetic stirrer, a kettle temperature probe, a cooling bath, a dropping funnel, a packed column, and a distillation head with N₂. Dicyclopentadiene (495.8 g, 3.75 mol) was added to the reactor and heated to reflux. N - allyl - aza - 2,2 - dimethoxysilacyclopentane (1404.8 g, 7.5 mol) was added dropwise to the reaction mixture over 1 - 2 hours at a rate that maintained the reaction temperature at 170 °C. The resulting reaction mixture was stirred at 170 - 180 °C for 72 hours. The product was purified by fractional distillation to obtain the final product N - [(5 - bicyclo[2.2.1]hept - 2 - enyl)methyl]aza - 2,2 - dimethoxysilacyclopentane (NB - CAZ - 1), 344 g (18.1%), purity 99.1%.

[0134] Example 2: Deposition of a monolayer of NB - CAZ - 1 on the silica surface

[0135] Silicon wafer specimens with a 110 crystal orientation and a native oxide layer were cleaned with oxygen plasma for ten minutes to remove organic contaminants. Then the specimens were placed in a stainless - steel vacuum container with a volume of about 250 ml. The system was evacuated at 25 °C for five minutes. Then the system was filled with nitrogen, and 50 μl of NB - CAZ - 1 was added to a position near the specimens in the container. Then the system was evacuated for one minute, after which the system was isolated from the pump and kept under static vacuum at 25 °C for thirty minutes. The specimens were rinsed with ethanol to remove any physically adsorbed materials. The thickness of the organic layer was measured to be 1.4 nm by ellipsometry, and the presence of 4.2% nitrogen on the surface was confirmed by X - ray photoelectron spectroscopy (XPS).

[0136] Example 3: Attachment of PEG - azide to the NB - CAZ - 1 functionalized surface

[0137] 8 - arm PEG - azide with a molecular weight of about 40,000 and a hydrodynamic radius of about 4 nm was dissolved in a 95 / 5 water / ethanol solution at a concentration of 0.5%. The specimens with an area of about 5 cm² prepared by the method of Example 2 2The sample was coated with 0.4 ml of PEG-azide solution, dried, and then cured in an oven at 70 °C for one hour. The sample was then sonicated in deionized water for ten minutes and then rinsed with deionized water to remove unbound PEG-azide. An organic layer of 9.25 nm was detected by ellipsometry, and the presence of PEG-azide was confirmed by XPS (62% oxygenated carbon, 33% oxygen, 1% nitrogen, and 4% silicon from the underlying substrate and NB-CAZ-1 layer).

[0138] Example 4: Deposition of NB-CAZ-1 on an aluminum substrate by solvent deposition

[0139] 0.0415 grams of N-[(5-bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane (NB-CAZ-1) was added to 1.95 grams of dry heptane and mixed on a FlackTek 330-100PRO centrifugal mixer at 3500 rpm for 20 seconds. The mixture was dropped onto a 2024T3 aluminum plate in liquid form and wiped with a cleanroom wipe. Analysis showed a 10 nm thick film containing norbornene detected by XPS.

[0140] Comparative Example 1: Connecting PEG-azide without using NB-CAZ-1

[0141] A silicon wafer sample of about 5 cm 2 was plasma cleaned in the same manner as in Example 1. Without exposure to NB-CAZ-1, 8-arm PEG-azide was then coated according to the method of Example 3. No PEG-azide layer was observed by either ellipsometry or XPS.

[0142] Those skilled in the art should understand that the above embodiments can be changed without departing from their broad inventive concept. In addition, based on the present invention, those of ordinary skill in the art will further recognize that the relative proportions of the above components can be changed without departing from the scope of the present invention. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A norbornene compound having the formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI): Among them, p is 0, 1 or 2; Q1 and Q2 are independently O, S, N(R 13 ), C=O, C(R 14 )(R 15 ) or (R 14 )(R 15 )C-C-(R 16 )(R 17 ); J1 and J2 are independently O, S, N(R 18 ), C=O or C(R 19 )(R 20 ); J3 is N or C(R 19 ); R 11 a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group or a (C6-C14) aromatic group that is bonded to both J1 and J2, or has the formula [T]: wherein, T1, T2, T3 and T4 are each independently selected from the group consisting of: O, S, N(R 21 ), C═O and C(R 22 )(R 23 ), each of S1, S2, S3 and S4 is 0 or 1, provided that S1 + S2 + S3 + S4 > 0; wherein if S1 + S2 + S3 + S4 ≥ 2, then [T] is a bidentate ligand bonded to both J1 and J2; R 12 is a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both J3 and J2, or has the formula [U]: wherein, U1 is N or C(R 22 ); U2, U3, and U4 are each independently selected from the group consisting of: O, S, N(R 21 ), C═O, and C(R 22 )(R 23 ), each of S5, S6, and S7 is 0 or 1; wherein if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bonded to both J1 and J3; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are the same or different and each independently selected from the group consisting of: a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tri(C1-C6)alkylsilyl, tri(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6)acyl, (C2-C8)acyloxy, (C6-C 14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14 ) aryl(C1-C6)alkoxy, (C1-C 12 ) alkyl(C1-C 12 ) perfluoro group, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 at least one of which contains or is substituted by a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) or formula (H): wherein Z is a Group 14 element other than carbon; X is a Group 15 element; Y is a Group 16 element; m and n are each independently an integer from 1 to 10; K1 and K2 are independently O, S, N(R 34 ), or C(R 35 )(R 36 ); R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group bonded to both J1 and J2, or has the formula [W]: wherein, W1, W2, W3, and W4 are each independently selected from the group consisting of: O, S, N(R 37 ), C═O, and C(R 39 )(R 39 ), each of S8, S9, S 10 , and S 11 is 0 or 1, provided that S8 + S9 + S 10 + S 11 > 0; wherein if S8 + S9 + S 10 + S 11 ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2; R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 34 、R 35 、R 36 、R 37 、R 38 and R 39 are the same or different and each independently is a single bond, hydrogen, halogen, hydroxyl, methyl, ethyl, methoxy, ethoxy, linear or branched (C3-C 18 ) alkyl, (C2-C 18 ) alkenyl, (C3-C 18 ) alkoxy, tris(C1-C6)alkylsilyl, tris(C1-C6)alkoxysilyl, di(C1-C6)alkylamino, di(C1-C6)alkyl(C1-C6)alkylamino, perfluoro(C1-C 18 ) alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) bicyclo(C1-C6)alkyl, (C7-C 14 ) tricyclo(C1-C6)alkyl, (C1-C 18 ) thioalkyl, (C2-C6) acyl, (C2-C8) acyloxy, (C6-C 14 ) aryl, (C6-C 14 ) aryl(C1-C8)alkyl, perfluoro(C6-C 14 ) aryl, perfluoro(C6-C 14 ) aryl(C1-C3)alkyl, (C6-C 14 ) aryloxy, (C6-C 14 ) aryl(C1-C6)alkoxy or (C1-C 12 ) alkyl(C1-C 12 ) perfluoro group; where R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 34 、R 35 、R 36 、R 37 、R 38 and R 39 At least one of them is a single bond connected to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI).

2. The norbornene compound according to claim 1, wherein, Z is silicon or germanium.

3. The norbornene compound according to claim 1 or 2, wherein X is nitrogen.

4. The norbornene compound according to any one of claims 1 to 3, characterized in that, Y is sulfur, selenium or tellurium.

5. The norbornene compound according to any one of claims 1 to 4, characterized in that, p = 0, m = 1 and n = 1.

6. The norbornene compound according to any one of claims 1 to 5, characterized in that, R 24 is a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl or tert-butyl, R 25 and R 26 is a single bond, hydrogen, methyl, methoxy or ethoxy, R 27 , R 28 , R 29 , R 30 , R 31 and R 32 are independently a single bond, hydrogen or methyl, Z is silicon, X is nitrogen or Y is sulfur.

7. The norbornene compound according to any one of claims 1 to 6, characterized in that The compound is N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane or N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-diethoxysilacyclopentane.

8. The norbornene compound according to any one of claims 1 to 7, having a structure selected from the group consisting of:

9. A method for preparing a norbornene-functionalized surface, comprising: Exposing a substrate having a hydroxyl surface group to the norbornene compound according to any one of claims 1 to 8.

10. The method according to claim 9, comprising: The norbornene compound is exposed to the substrate in the gas phase.

11. The method according to claim 10, wherein The gas phase exposure is carried out at a temperature below about 80 °C.

12. The method according to claim 11, wherein The gas phase exposure is carried out at a temperature below about 50 °C.

13. The method according to claim 12, wherein The gas phase exposure is carried out at a temperature below about 30 °C.

14. The method according to claim 9, comprising: The norbornene compound is exposed to the substrate in the liquid phase.

15. The method according to claim 14, wherein The liquid phase exposure includes spin coating, dip coating, coating on the substrate by wiping a liquid or spraying.

16. A method of preparing a reactive polymer layer bonded to a substrate, the method comprising: Coating the norbornene-functionalized surface according to claim 9 with a polymer containing norbornene-reactive functional groups.

17. The method according to claim 16, wherein The polymer containing norbornene-reactive functional groups contains azide, thiol or tetrazine functional groups.

18. The method according to claim 16, wherein The polymer containing norbornene-reactive functional groups is coated on the norbornene-functionalized surface by spin coating, dip coating, coating on the substrate by wiping a liquid or spraying.

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