Cycloalkylnorbornene compounds with heterocyclic functional groups for fast, low-temperature, low-VOC surface functionalization

Abstract

A series of norbornene compounds with heterocyclic functional groups and methods for their preparation are described, as well as a fast, low-temperature, low-VOC method for attaching these norbornene compounds to surfaces for use as chemical attachment points for various functional molecules.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to pending U.S. Provisional Application No. 63 / 429,193, filed December 1, 2022, the disclosure of which is incorporated herein by reference. Summary of the Invention [Problem to be solved by the invention]

[0002] Norbornene units have long been used to impart superior properties to polymer systems due to their rigid structure. The use of norbornene units results in high glass transition temperatures, which are important for many applications. Furthermore, unlike chemically similar compounds such as vinyl or allyl groups, norbornene units exhibit high reaction selectivity, allowing them to be used, for example, to attach reactive polymers to glass or polymer substrates in biomolecule detection, proteomics, and nucleic acid sequencing applications. The ability to easily surface-attach norbornene-containing compounds using a rapid, low-temperature, low-VOC process reduces environmental impact, material consumption, and capital costs, while enabling the application of norbornene functional groups on substrates with limited temperature stability. [Means for solving the problem]

[0003] In one embodiment, the disclosed aspects are represented by Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), or Formula (VI): [ka] where 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 )CC-(R 16 )(R 17 ) and J1 and J2 are independently O, S, N(R 18), C=O, or C(R 19 )(R 20 ) and J3 is N or C(R 19 ) and;

[0004] 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 a group represented by the formula [T]: [ka] (In the formula, T1, T2, T3, and T4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ) where S1, S2, S3, and S4 are each 0 or 1 provided that S1+S2+S3+S4>0; if S1+S2+S3+S4≧2, then [T] is a bidentate ligand bound to both J1 and J2. having;

[0005] R 12 is a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both J3 and J2, or a group represented by the formula [U]: [ka] (Wherein U1 is N or C(R 22 ) and U2, U3, and U4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), wherein S5, S6, and S7 are each 0 or 1; if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bound to both J1 and J3. having;

[0006] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R18 , R 19 , R 20 , R 21 , R 22 , and R 23 are the same or different, and each independently represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, 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 the formulas is (A), (B), (C), (D), (E), (F), (G), or (H): [ka]

[0007] (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 ) and R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group, or a group represented by the formula [W]: [ka] (Wherein W1, W2, W3, and W4 are each independently O, S, N(R 37 ), C=O and C(R 39 )(R 39 ) is selected from S8+S9+S 10 +S 11 >0, S8, S9, S 10 and S 11 are each 0 or 1; S8 + S9 + S 10 +S 11 If ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2. containing or substituted with a heterocyclic group having the formula:

[0008] 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 39are the same or different, and each independently represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, or (C1-C 12 ) Alkyl (C1-C 12 ) perfluoro; 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 is a single bond bonding to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI). The present invention relates to a norbornene compound having the formula:

[0009] Advantageous refinements of the invention, implemented singly or in combination, are specified in the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0010] In summary, the following embodiments are presented as particularly preferred embodiments within the scope of the present invention:

[0011] Embodiment 1: Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), or Formula (VI): [ka] where 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 )CC-(R 16 )(R 17 ) and J1 and J2 are independently O, S, N(R 18 ), C=O, or C(R 19 )(R 20 ) and J3 is N or C(R 19 ) and;

[0012] 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 a group represented by the formula [T]: [ka] (In the formula, T1, T2, T3, and T4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ) where S1, S2, S3, and S4 are each 0 or 1 provided that S1+S2+S3+S4>0; if S1+S2+S3+S4≧2, then [T] is a bidentate ligand bound to both J1 and J2. having;

[0013] R 12 is a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both J3 and J2, or a group represented by the formula [U]: [ka] (Wherein U1 is N or C(R 22 ) and U2, U3, and U4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), wherein S5, S6, and S7 are 0 or 1; if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bound to both J1 and J3. having;

[0014] 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 represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, 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 the formulas is (A), (B), (C), (D), (E), (F), (G), or (H): [ka]

[0015] (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 ) and R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group, or a group represented by the formula [W]: [ka] (Wherein W1, W2, W3, and W4 are each independently O, S, N(R 37 ), C=O and C(R 39 )(R 39 ) is selected from S8+S9+S10 +S 11 >0, S8, S9, S 10 and S 11 are each 0 or 1; S8 + S9 + S 10 +S 11 If ≥ 2, then [W] is a bidentate ligand bonded to both K1 and K2. containing or substituted with a heterocyclic group having the formula:

[0016] 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 represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, or (C1-C 12 ) Alkyl (C1-C 12 ) perfluoro; 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 is a single bond bonding to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI). A norbornene compound having the formula:

[0017] Embodiment 2: The norbornene compound of embodiment 1, wherein Z is silicon or germanium.

[0018] Embodiment 3: The norbornene compound of embodiment 1 or 2, wherein X is nitrogen.

[0019] Embodiment 4: The norbornene compound of any of embodiments 1 to 3, wherein Y is sulfur, selenium, or tellurium.

[0020] Embodiment 5: The norbornene compound of any one of embodiments 1 to 4, wherein p=0, m=1, and n=1.

[0021] Embodiment 6: R 24 is a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl, or t-butyl, and R 25 and R 26 is a single bond, hydrogen, methyl, methoxy, or ethoxy, and R 27 , R 28 , R 29 , R 30 , R 31, and R 32 are independently a single bond, hydrogen, or methyl; Z is silicon; and X is nitrogen or Y is sulfur.

[0022] Embodiment 7: The norbornene compound of any one of embodiments 1 to 6, which is N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane or -[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-diethoxysilacyclopentane. [ka]

[0023] Embodiment 8: [ka] The norbornene compound of any one of embodiments 1 to 7, having a structure selected from

[0024] Embodiment 9: A method of forming a norbornene-functionalized surface, comprising contacting a substrate comprising a hydroxyl group on its surface with a norbornene compound according to any one of embodiments 1 to 8.

[0025] Embodiment 10: The method of embodiment 9, comprising contacting the norbornene compound with the substrate in the vapor phase.

[0026] Embodiment 11: The method of embodiment 10, wherein the vapor phase contacting occurs at less than about 80°C.

[0027] Embodiment 12: The method of embodiment 11, wherein the vapor phase contacting occurs at less than about 50°C.

[0028] Embodiment 13: The method of embodiment 12, wherein the gas-phase contacting occurs at less than about 30°C.

[0029] Embodiment 14: The method of embodiment 9, comprising contacting the norbornene compound with the substrate in a liquid phase.

[0030] Embodiment 15: The method of embodiment 14, wherein the liquid-phase contacting comprises spin-coating, dip-coating, applying by wiping the liquid onto the substrate, or spray-coating.

[0031] Embodiment 16: A method of forming a reactive polymer layer attached to a substrate, comprising coating a norbornene-functionalized surface according to embodiment 9 with a polymer comprising norbornene-reactive functional groups.

[0032] Embodiment 17: The method of embodiment 16, wherein the polymer comprising norbornene-reactive functional groups comprises azide, thiol, or tetrazine functional groups.

[0033] Embodiment 18: The method of embodiment 16, wherein the polymer comprising norbornene-reactive functional groups is coated onto the norbornene-functionalized surface by spin coating, dip coating, applying by wiping a liquid onto the substrate, or spray coating.

[0034] Detailed Description of the Invention Aspects of the present disclosure relate to a series of norbornene compounds with heterocyclic functional groups and a fast, volatile organic compound (VOC)-free or low-VOC method for adhering these norbornene compounds to surfaces. In some embodiments, the disclosure relates to a series of cyclic azasilane and thiasilane compounds that employ norbornene or heterocyclic functional groups and have application as VOC-free or low-VOC, fast, and selective surface functionalization agents.

[0035] Unless otherwise specified, numerical values ​​set forth herein should be understood to be modified by "about" in all instances. Thus, numerical values ​​typically include ±10% of the stated value. For example, a description of a temperature such as "10°C" or "about 10°C" includes 9°C and 11°C and all temperatures therebetween. Furthermore, all numerical ranges provided in this disclosure expressly encompass all subranges and include all individual numerical values ​​within that range, including integers and fractions and decimals within that range, unless the context clearly indicates otherwise. All carbon chain length ranges are understood to encompass all carbon chain lengths within the stated range. For example, "linear or branched (C3-C18) alkyl" may be understood to refer to all linear and branched alkyl groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms.

[0036] norbornene compounds As described in more detail below, embodiments of the present disclosure relate to norbornene-containing compounds with heterocyclic functional groups suitable for forming surfaces containing norbornene functional groups. Norbornene is a highly strained, bridged cyclic hydrocarbon consisting of a cyclohexene ring and a methylene bridge between the 1- and 4-carbon positions. The simplest norbornene compound, bicyclo[2.2.1]hept-2-ene, has the following structure (showing two different renderings of the same molecule): [ka] It has.

[0037] More broadly, the present disclosure provides a compound of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI): [ka] The present invention relates to a norbornene compound having the formula:

[0038] 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 )CC-(R 16 )(R 17 ) and J1 and J2 are independently O, S, N(R 18 ), C=O, or C(R 19 )(R 20 ) and J3 is N or C(R 19 ) and;

[0039] 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 a group represented by the formula [T]: [ka] (In the formula, T1, T2, T3, and T4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ) where S1, S2, S3, and S4 are each 0 or 1 provided that S1+S2+S3+S4>0; if S1+S2+S3+S4≧2, then [T] is a bidentate ligand bound to both J1 and J2. having;

[0040] R 12 is a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both J3 and J2, or a group represented by the formula [U]: [ka] (Wherein U1 is N or C(R 22 ) and U2, U3, and U4 are each independently O, S, N(R 21 ), C=O and C(R 22 )(R 23 ), wherein S5, S6, and S7 are each 0 or 1; if S5 + S6 + S7 ≥ 1, then [U] is a bidentate ligand bound to both J1 and J3. having;

[0041] 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 represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R18 , R 19 , R 20 , R 21 , R 22 , and R 23 At least one of the formulas is (A), (B), (C), (D), (E), (F), (G), or (H): [ka] The heterocyclic group may contain or be substituted with a heterocyclic group having the formula:

[0042] 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 ) and R 33 is a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group, or a group represented by the formula [W]: [ka] (Wherein W1, W2, W3, and W4 are each independently O, S, N(R 37 ), C=O and C(R 39 )(R 39 ) is selected from S8+S9+S 10 +S 11 >0, S8, S9, S 10 and S 11 are each 0 or 1; S8 + S9 + S 10 +S 11 If ≥ 2, then [W] is a bidentate ligand bound to both K1 and K2. having;

[0043] 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 are the same or different, and each independently represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (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, or (C1-C 12 ) Alkyl (C1-C 12 ) perfluoro; 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 is a single bond connecting to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI).

[0044] In formula (I), formula (II), formula (III), formula (IV), formula (V), and formula (VI), Q1 and Q2 form a bridge of a norbornene structure, and are preferably, but not limited to, CH2, C(CH3)2, O, N(CH3), and CH2-CH2; p is 0, 1, or 2; 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 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, 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 each independently preferably, but not limited to, a single bond, hydrogen, methyl, vinyl, ethyl, n-propyl, or n-butyl; J1 and J2 are preferably independently NH, N(CH3), O, or CH2, and J3 is preferably N, CH, or C(CH3).

[0045] In a most preferred embodiment, the norbornene compound has formula (I), Q is CH, p=0, and R, ... 10 is hydrogen.

[0046] In formulas (A), (B), (C), (D), (E), (F), (G), and (H), Z is a Group 14 element other than carbon, such as, but not limited to, silicon or germanium; X is a Group 15 element, such as, but not limited to, nitrogen or phosphorus; and Y is a Group 16 element, such as, but not limited to, sulfur, selenium, tellurium, etc. Thus, each of the functional groups (A) through (H) has a bond between the Group 14 element (Z) and either the Group 15 element (X) or the Group 16 element (Y).

[0047] In formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), and formula (H), 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 must be a single bond connecting to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI). 24 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R38 , and R 39 are independently, but are not limited to, preferably a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl, or t-butyl; R 25 and R 26 is independently preferably a single bond, hydrogen, methyl, ethyl, methoxy, or ethoxy.

[0048] In a preferred embodiment, the heterocyclic component structure has formula (A) or formula (B), m=1 or 2, n=1 or 2, and R 24 , R 27 , R 28 , and R 29 are independently a single bond, hydrogen, or methyl; R 25 and R 26 is a single bond, hydrogen, methyl, methoxy, or ethoxy, Z is silicon, X is nitrogen, and Y is sulfur.

[0049] In the most preferred embodiment, the heterocyclic moiety structure has formula (A), m=1, n=1, and R 24 , R 27 , R 28 , and R 29 are independently a single bond, hydrogen, or methyl; R 25 and R 26 is a single bond, hydrogen, methyl, methoxy, or ethoxy, Z is silicon, and X is nitrogen.

[0050] In the case of compounds having formula (E), formula (F), formula (G), and formula (H), the bridge structure is formed by groups K1, K2, and R 33 and which are bonded to both K1 and K2, and are a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group, or a (C6-C14) aromatic group, or are represented by the formula [W] defined above: [ka] K1 and K2 are preferably independently selected from NH, N(CH3), O, or CH2.

[0051] In preferred compounds including Formula (E), Formula (F), Formula (G), and Formula (H), K1 and K2 are O, S8 and S9 are 1, S10 and S11 are 0, and W1 and W2 are CH2, CH(CH3), or C(CH3)2.

[0052] The difference between norbornene compounds having formula (I) and formula (II) is that the former has four independent ligands R, R, R, and R (typically two or three of which are hydrogen), whereas the latter has a cyclic substituent (J-R) that consumes two coordination sites. 11 The difference between formula (II) and formula (III) is that J3 has R 12 While J2 has a double bond to the adjacent atom in R 11 The atom has a single bond to a neighboring atom.

[0053] Similarly, the difference between norbornene compounds having formula (IV) and formula (V) is that the former has two independent ligands, R2 and R3, whereas the latter has a cyclic substituent (J1-R 11 The difference between formula (V) and formula (VI) is that J3 has R 12 While J2 has a double bond to the adjacent atom in R 11 The atom has a single bond to a neighboring atom.

[0054] The difference between formulas (I), (II), and (III), and the difference between formulas (IV), (V), and (VI), is the presence of a double bond instead of the independent substituents R and R.

[0055] Examples of compounds having formula (I) where p=0 and p=1 are shown below in formulas (VII) and (VIII), respectively. For compounds having formula (VII), the variables in formula (I) are as follows: p=0 and Q1=C(R 14 )(R 15 ) and R 14 =R 15=H, m=n=1, and R 25 =R 26 =CH3, and R 27 =R 28 =R 29 =H, Z=Si, X=N, and R2, R3, R4, R7, R8, R9, and R 10 =H, R1 = a methyl group substituted with a compound having formula (A), and R 24 is a single bond connecting the heterocyclic group to the norbornene portion of the structure having formula 1. For compounds having formula (VIII), the variables in formula (I) are as follows: p=1, Q1=Q2=C(R 14 )(R 15 ) and R 14 =R 15 =H, m=n=1, and R 25 =R 26 =CH3, and R 27 =R 28 =R 29 =H, Z=Si, X=N, and R2, R3, R4, R5, R6, R7, R8, R9, and R 10 =H, R1 = a methyl group substituted with a compound having formula (A), and R 24 is a single bond connecting the heterocyclic group to the norbornene portion of the structure having formula (I). [ka]

[0056] Examples of compounds having formula (II) or formula (III) in which J1, J2, and J3 contain carbon, nitrogen, and oxygen are shown in formula (IX), formula (X), and formula (XI), respectively. [ka]

[0057] For compounds having formula (IX), the variables in formula (II) are as follows: p=0 and Q1=C(R 14 )(R 15 ) and R 14 =R15 =H, and J1 = CH(R 20 ) and R 20 is a single bond connecting to the heterocycle of type A, J2=CH2, and 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, and R 27 = a single bond that binds to a compound having formula (II). In formula (X), p=0 and Q1=C(R 14 )(R 15 ) and R 14 =R 15 =H, and J1 = N(R 18 ) and R 18 is a single bond attached to the heterocycle of type A, and R 12 =N(S5=S6=S7=0, U1=N), and R 25 =R 26 =CH3; R1, R4, R7, R8, R9, R 10 , R 24 , R 28 , and R 29 =H, and R 27 = a single bond bonded to a compound having formula (III). In formula (XI), p=0 and Q1=C( 14 )(R 15 ) and R 14 =R 15 =H, J1 = J2 = O, and R5 = CH(R 23 )(S1=1, S2=S3=S4=0, T1=CH(R 23 )) and R 23 = single bond attached to the heterocycle of type A, R 25 =R 26 =CH3; R1, R4, R7, R8, R9, R 10 , R 24 , R 28 , and R 29 =H, and R 27= is a single bond attached to a compound having formula (II).

[0058] Considering the heterocyclic portion of norbornene compounds, there are three key variables in the core structure, leading to eight possible functional groups with formulas (A) through (H).

[0059] The first variable is a simple ring or "silatrane" that contains a nitrogen atom in a chain that forms a weak bond with the Z atom (typically silicon) to form the pseudo-bicyclic structures of formula (C), formula (D), formula (G), and formula (H). Functional groups (A), (B), (E), and (F) contain simple cyclic groups.

[0060] Examples of norbornene compounds containing a simple cyclic group (formula (A)) and a silatrane group (formula (C)) are shown in formulas (XII) and (XIII): [ka]

[0061] The second variable refers to the Z moiety (typically silicon) and has two bonds that are not part of a ring. These can be independent ligands, such as alkoxy or alkyl, or bidentate bridging structures that consume both sites, such as in group (E) to group (H).

[0062] An example of a norbornene compound having a bidentate ligand and a functional group (E) has the formula (XIV): In formula (E), K1 and K2 are oxygen, and R 33 is a (C6) aryl group attached to both K1 and K2: [ka]

[0063] The third variable relates to the X / Y moiety (typically nitrogen or sulfur), and in the case of nitrogen, the third bond (R 14), whereas in the case of sulfur or other Group 16 elements, there is no third bond. These differences are depicted in formula (A) versus formula (B), formula (C) versus formula (D), etc. For example, compound (XV) below has a substituent X (here, nitrogen), while compound (XVI) below has a substituent Y (here, sulfur). [ka]

[0064] The compounds disclosed in the present invention include a norbornene moiety as shown in formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (IV), 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 the heterocyclic groups of formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), or formula (H) contains or is substituted with a heterocyclic group having formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), or formula (H). "Containing" 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 bonded to the norbornene moiety shown in formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (IV) by a single bond, and 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 Position of the heterocyclic group R 24 , R 25 , R 26 , R27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 34 , R 35 , R 36 , R 37 , R 38 , and R 39 In this case, the norbornene group and the heterocyclic group may be considered to be directly bonded to each other.

[0065] 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 When the heterocyclic group having the formula (A), the formula (B), the formula (C), the formula (D), the formula (E), the formula (F), the formula (G), or the formula (H) is contained, the bonding positions of the norbornene moiety 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 is 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, where R groups and positions R of the heterocyclic group are interchangeable at any chemically appropriate position of the R 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 In this case, the norbornene group and the heterocyclic group are bonded to each other by R1, R2, R3, R4, R5, R6, R7, R8, R9, and 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 They may be considered to be linked by a bridging group containing

[0066] Formulas (XVII), (XVIII), (XIX), and (XX) below show the difference between directly bonded norbornene groups and heterocyclic groups and those bonded via a bridging group. In the directly bonded formula (XVII), a single bond is formed between the position R4 of the norbornene group in formula (I) and the position R4 on the nitrogen atom of the heterocyclic group in formula (A). 24 and in formula (XVIII), the single bond is present between the norbornene group in formula (I) and the R 14 and the position R on the silicon atom of the heterocyclic group of formula (A). 25 It exists between.

[0067] Formula (XIX) and Formula (XX) show examples of linkage via a bridging group. In the bridged formula (XIX), the methyl group substituted with the heterocyclic group of formula (A) is located at position R1 of the norbornene group, and the methyl group is located at position R2 on the nitrogen atom of the heterocyclic group. 24 In the bridged formula (XX), a (C6) aryl (phenyl) group is located at position R4 of the norbornene group, and the (C6) aryl group is substituted meta to the heterocyclic group of formula (A), and the (C6) aryl group is attached to a carbon atom of the heterocyclic group at position R 27 are bonded by a single bond. [ka]

[0068] The compounds disclosed herein may have two or more heterocyclic groups of formula (A), (B), (C), (D), (E), (F), (G), or (H), as shown in formula (XXI) below, or two or more norbornene groups of formula (I), (II), (III), (IV), (V), or (IV), as shown in formula (XXII) below. In compounds having two or more heterocyclic groups, the heterocyclic groups may be the same or different and are bonded to one or more norbornene groups at positions defined above. Similarly, in compounds having two or more norbornene groups, the norbornene groups may be the same or different and are bonded to one or more heterocyclic groups at positions defined above. [ka]

[0069] Representative examples of norbornene-heterocyclic compounds according to embodiments of the present disclosure are shown below. [ka]

[0070] Although the formulas and structures depicted herein do not imply stereochemistry unless otherwise specified, the norbornene compounds depicted herein include mixtures of diastereomers that generally retain their configuration upon reaction of the double bond by the methods described below. The diagram below representatively shows the R and S enantiomers of the exo and endo isomers of the norbornene structures of the present invention, which result from the attachment of two different groups at the C4 or C5 carbon of norbornene. Because these exo and endo isomers and their enantiomers may have different properties, it should be understood that it is within the scope of the present disclosure to take advantage of these differences in properties by using essentially pure exo or endo isomers, or R or S enantiomers, or mixtures enriched in either isomer or enantiomer. [ka]

[0071] surface functionalization A further embodiment of the present disclosure relates to the functionalization of surfaces with norbornene groups by a rapid, VOC-free or low VOC method using appropriate heterocyclic groups that undergo ring-opening reactions with hydroxyl groups of target substrates.

[0072] More particularly, embodiments of the present disclosure relate to the bonding of norbornene compounds described herein to (a) substrates having surface hydroxyl groups, such as glass, quartz, alumina, and titania; (b) polymeric substrates that inherently have surface hydroxyl groups as part of their chemical structure, such as epoxy or urethane resins; or (c) substrates that have been treated to provide surface hydroxyl groups using techniques such as ozone oxidation, ozone / UV treatment, plasma treatment, or corona treatment of silicone, polyester, polystyrene, butadiene rubber, polyethylene, or polypropylene.

[0073] It is known in the art that norbornene groups can be attached to the aforementioned substrates through the use of trialkoxysilyl-functionalized norbornenes, such as [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane. However, the reaction kinetics of these molecules are slow, requiring time periods on the order of an hour and elevated deposition temperatures of approximately 100°C to achieve sufficient coverage for most applications. In addition, a post-cure step of approximately 1 hour at 100°C is typically required to further condense the remaining alkoxy groups to their final stable state. Furthermore, exposure to these compounds typically results in excess material being physisorbed onto the substrate surface, necessitating an additional removal step prior to the curing step. Additionally, the reaction chemistry of the deposition step involves the production of volatile organic components, in this case methanol, which further poses process safety and environmental concerns.

[0074] However, the norbornene heterocycles described herein, which include norbornene chemically bonded to the heterocycle by a bond between a Group 14 element and either a Group 15 element or a Group 16 element, undergo rapid ring opening in the presence of hydroxyl groups and can be used to attach the norbornene functionality to hydroxyl-containing substrates without the concomitant release of VOCs.

[0075] It should be understood that the use of the heterocyclic compounds of the present invention in reactions with hydroxylated surfaces is useful without the release of any volatile organic compounds (VOCs), such as methanol or ethanol. If the heterocyclic compounds of the present invention do not contain alkoxide or other reactive groups, the use of the compounds in the processes of the present invention is VOC-free. However, if the molecules of the present invention contain alkoxy or other reactive groups that can cause side reactions, VOCs may be released during reaction or curing. In this case, the processes of the present invention are low VOC compared to comparable processes that release alcohol during the initial reaction with the substrate and subsequent reaction or curing.

[0076] A method for forming a norbornene-functionalized surface according to an embodiment of the present disclosure thus comprises contacting a substrate containing surface hydroxyl groups with a norbornene compound described herein. This contacting can be gas-phase contacting by any method known in the art, such as chemical vapor deposition, by exposing the substrate to vapors of a compound of the present invention at temperatures below about 80° C., more preferably below about 50° C., and most preferably below about 30° C., for a timescale of less than about 1 hour. Liquid-phase contacting, in which the norbornene compound is optionally dissolved in a non-hydrolytic solvent such as toluene, tetrahydrofuran, or dimethoxyethane, can be performed by spin-coating, dip-coating, wiping, spray-coating, or other methods known in the art.

[0077] Scheme 1 shows the functionalization of a hydroxylated surface with norbornene groups according to this method. [ka]

[0078] Use of norbornene-functionalized surfaces as coupling agents. In another embodiment of the present disclosure, surfaces coated with the compounds of the present invention can be used to attach molecules or polymers reactive with norbornene groups. Such molecules or polymers, known in the art, contain reactive groups such as azide, thiol, or tetrazole, which are known to react with norbornene groups via rapid "click" chemistry. The norbornene groups can be used to directly attach to appropriately functionalized molecules of interest, as shown in Scheme 2, or can be attached to an appropriately functionalized binding layer, which can then be attached to an appropriately functionalized target molecule, as shown in Scheme 3. Target molecules can include, but are not limited to, molecules used for detecting, reacting with, or binding 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. [ka]

[0079] In Scheme 2 and Scheme 3, "X" represents a norbornene-reactive group such as an azide, thiol, or tetrazole, and in Scheme 3, "Y" represents a group reactive with norbornene or a norbornene-reactive group such as an alkyne. [ka]

[0080] Azide, thiol, and tetrazole groups suitable for attachment to norbornene-functionalized surfaces are shown below, where R represents an organic or organic / inorganic chemical compound. [ka] [Example]

[0081] The invention will now be described with reference to the following non-limiting examples.

[0082] Example 1: Synthesis of N-[(bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane [ka] A 1 L four-neck flask was equipped with a magnetic stirrer, thermometer, cooling bath, addition funnel, packed column, and distillation head and purged with nitrogen. Dicyclopentadiene (495.8 g, 3.75 mol) was charged to the reaction vessel 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 yield the final product, N-[(5-bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane (NB-CAZ-1), 344 g (18.1%), 99.1% purity.

[0083] Example 2: Deposition of NB-CAZ-1 monolayers onto silicon dioxide surfaces A 110-oriented silicon wafer sample with native oxide was cleaned with oxygen plasma for 10 minutes to remove organic contaminants. The sample was then placed in a stainless steel vacuum chamber with a volume of approximately 250 mL and evacuated for 5 minutes at 25°C. The system was then filled with nitrogen, and 50 μL of NB-CAZ-1 was added to the chamber adjacent to the sample. The system was then evacuated for 1 minute, isolated from the pump, and placed under static vacuum at 25°C for 30 minutes. The sample was then rinsed with ethanol to remove any physisorbed material. A 1.4 nm thick organic layer was measured by ellipsometry, and X-ray photoelectron spectroscopy (XPS) confirmed the presence of 4.2% nitrogen on the surface.

[0084] Example 3: Conjugation of PEG-azide to NB-CAZ-1 functionalized surfaces An 8-arm PEG-azide having a molecular weight of approximately 40,000 and a hydrodynamic radius of approximately 4 nm was dissolved in a 95 / 5 water / ethanol solution at a concentration of 0.5%. 2 A sample with an area of ​​10 nm was coated with 0.4 mL of PEG-azide solution, dried, and then cured in a drying oven at 70 °C for 1 h. The sample was then sonicated in deionized water for 10 min and then washed with deionized water to remove unbound PEG-azide. A 9.25 nm organic layer was detected by ellipsometry, and the presence of PEG-azide was confirmed by XPS (62% oxygenated carbon, 33% oxygen, 1% nitrogen, and 4% silicon in the underlying substrate and NB-CAZ-1 layer).

[0085] Example 4: Deposition of NB-CAZ-1 onto aluminum substrates by solvent deposition 0.0415 g of N-[(5-bicyclo[2.2.1]hept-2-enyl)methyl]aza-2,2-dimethoxysilacyclopentane (NB-CAZ-1) was added to 1.95 g of anhydrous heptane, and the mixture was mixed in a FlackTEK 330-100PRO centrifugal mixer at 3500 rpm for 20 seconds. The mixture was dispensed in liquid form onto 2024T3 aluminum foil and wiped with cleanroom wipes. XPS analysis revealed a 10 nm thick film containing norbornene.

[0086] Comparative Example 1: Conjugation of PEG-azide without NB-CAZ-1 Approximately 5cm 2 A silicon wafer sample was plasma cleaned in the same manner as in Example 1. Without exposure to NB-CAZ-1, the sample was coated with 8-arm PEG-azide according to Example 3. No PEG-azide layer was observed by ellipsometry or XPS.

[0087] It will be understood by those skilled in the art that the above-described embodiments may be modified without departing from the broad concept of the present invention. Furthermore, based on the present disclosure, a person skilled in the art will further appreciate that the relative amounts of the above-described components may be varied without departing from the spirit and scope of the present invention. It is therefore understood that the present invention is not limited to the specific embodiments disclosed, but also encompasses modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), or Formula (VI): 【Chemistry 1】 wherein p is 0, 1 or 2; Q １ and Q ２ 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 ) and J １ and J ２ are independently O, S, N (R １８ ), C═O, or C(R １９ ) (R ２０ ) and J ３ is N or C(R １９ ) and R １１ Is J １ and J ２ or a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, or a (C6-C14) aromatic group bonded to both of the 【Chemistry 2】 (In the formula, T １ , T ２ , T ３ and T ４ are each independently O, S, or N(R ２１ ), C═O and C(R ２２ ) (R ２３ ) and S １ , S ２ , S ３ and S ４ is S １ +S ２ +S ３ +S ４ >0, each of which is 0 or 1; S １ +S ２ +S ３ +S ４ If ≧2, [T] is J １ and J ２ is a bidentate ligand bound to both having R １２ Is J ３ and J ２ or a (C5-C12) aliphatic group or a (C5-C12) heterocyclic group bonded to both of the 【Transformation 3】 (In the formula, U １ is N or C(R ２２ ) and U ２ , U ３ , and U ４ are each independently O, S, or N(R ２１ ), C═O and C(R ２２ ) (R ２３ ) and S ５ , S ６ , and S ７ are each 0 or 1; S ５ +S ６ +S ７ If ≧1, then [U] is J １ and J ３ is a bidentate ligand bound to both having R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , 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 represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (C ３ ~C １８ ) alkyl, (C ２ ~C １８ ) alkenyl, (C ３ ~C １８ ) alkoxy, tri(C １ ~C ６ ) alkylsilyl, tri(C １ ~C ６ ) alkoxysilyl, di(C １ ~C ６ ) alkylamino, di(C １ ~C ６ ) alkyl(C １ ~C ６ ) alkylamino, perfluoro(C １ ~C １８ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) Bicyclo(C １ ~C ６ ) alkyl, (C ７ ~C １４ ) tricyclo(C １ ~C ６ ) alkyl, (C １ ~C １８ ) thioalkyl, (C ２ ~C ６ ) acyl, (C ２ ~C ８ ) acyloxy, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) aryl (C １ ~C ８ ) alkyl, perfluoro(C ６ ~C １４ ) aryl, perfluoro(C ６ ~C １４ ) aryl (C １ ~C ３ ) alkyl, (C ６ ~C １４ ) aryloxy, (C ６ ~C １４ ) aryl (C １ ~C ６ ) alkoxy, (C １ ~C １２ ) alkyl(C １ ~C １２ ) perfluoro, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , 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 the formula (A), formula (B), formula (C), formula (D), formula (E), formula (F), formula (G), or formula (H): 【Chemistry 4】 【Transformation 5】 (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; K １ and K. ２ are independently O, S, N (R ３４ ), or C(R ３５ ) (R ３６ ) and R ３３ Is J １ and J ２ or a (C5-C12) aliphatic group, a (C5-C12) heterocyclic group, a (C6-C14) aromatic group, or a group represented by the formula [W]: 【Transformation 6】 (In the formula, W １ , W ２ , W ３ , and W ４ are each independently O, S, or N(R ３７ ), C═O and C(R ３９ ) (R ３９ ) and S ８ +S ９ +S １０ +S １１ >0, S ８ , S ９ , S １０ and S １１ are each 0 or 1; S ８ +S ９ +S １０ +S １１ If ≧2, [W] is K １ and K. ２ and a heterocyclic group having a bidentate ligand bonded to both 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 are the same or different, and each independently represents a single bond, hydrogen, halogen, hydroxy, methyl, ethyl, methoxy, ethoxy, straight-chain or branched (C ３ ~C １８ ) alkyl, (C ２ ~C １８ ) alkenyl, (C ３ ~C １８ ) alkoxy, tri(C １ ~C ６ ) alkylsilyl, tri(C １ ~C ６ ) alkoxysilyl, di(C １ ~C ６ ) alkylamino, di(C １ ~C ６ ) alkyl(C １ ~C ６ ) alkylamino, perfluoro(C １ ~C １８ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) Bicyclo(C １ ~C ６ ) alkyl, (C ７ ~C １４ ) tricyclo(C １ ~C ６ ) alkyl, (C １ ~C １８ ) thioalkyl, (C ２ ~C ６ ) acyl, (C ２ ~C ８ ) acyloxy, (C ６ ~C １４ ) aryl, (C ６ ~C １４ ) aryl (C １ ~C ８ ) alkyl, perfluoro(C ６ ~C １４ ) aryl, perfluoro(C ６ ~C １４ ) aryl (C １ ~C ３ ) alkyl, (C ６ ~C １４ ) aryloxy, (C ６ ~C １４ ) aryl (C １ ~C ６ ) alkoxy, or (C １ ~C １２ ) alkyl(C １ ~C １２ ) perfluoro; 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 is a single bond connecting to the structure of formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI). A norbornene compound having the formula:

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

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

4. 4. The norbornene compound according to claim 1, wherein Y is sulfur, selenium, or tellurium.

5. 5. The norbornene compound according to claim 1, wherein p=0, m=1, and n=1.

6. R ２４ is a single bond, hydrogen, methyl, ethyl, vinyl, isopropyl, n-propyl, allyl, n-butyl, sec-butyl, or t-butyl, and R ２５ and R ２６ is a single bond, hydrogen, methyl, methoxy, or ethoxy, and R ２７ , R ２８ , R ２９ , R ３０ , R ３１ , and R ３２ 6. The norbornene compound of claim 1, wherein: are independently a single bond, hydrogen, or methyl; Z is silicon; and X is nitrogen or Y is sulfur.

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

8. below: 【Transformation 8】 The norbornene compound according to claim 1 , having a structure selected from:

9. 9. A method of forming a norbornene-functionalized surface, comprising contacting a substrate containing surface hydroxyl groups with a norbornene compound according to any one of claims 1 to 8.

10. 10. The method of claim 9, comprising the step of vapor-phase contacting the norbornene compound with the substrate.

11. 11. The method of claim 10, wherein the vapor phase contacting is carried out at less than about 80°C.

12. 12. The method of claim 11, wherein the vapor phase contacting is carried out at less than about 50°C.

13. 13. The method of claim 12, wherein the vapor phase contacting is carried out at less than about 30°C.

14. 10. The method of claim 9, comprising the step of liquid-phase contacting a norbornene compound with a substrate.

15. 15. The method of claim 14, wherein the liquid phase contacting comprises spin coating, dip coating, applying by wiping the liquid onto the substrate, or spray coating.

16. 10. A method of forming a reactive polymer layer bonded to a substrate, comprising coating the norbornene-functionalized surface of claim 9 with a polymer containing norbornene-reactive functional groups.

17. 17. The method of claim 16, wherein the polymer comprising norbornene-reactive functional groups comprises azide, thiol, or tetrazine functional groups.

18. 17. The method of claim 16, wherein the polymer containing norbornene-reactive functional groups is coated onto the norbornene-functionalized surface by spin coating, dip coating, applying by wiping a liquid onto a substrate, or spray coating.

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