Patent Application
20240383933
Alkene and Alkyne metathesis catalysts are created by installing pendant alkene and alkyne groups on the ligand; however, traditional catalyst designs leave the metal-carbon multiple bond exposed which can cause formation of side-products or degradation of the catalyst. There is a need for catalysts that do not have an exposed metal carbon multiple bond. In addition, there is a need for catalysts that polymerize alkynes and/or alkenes by ring expansion metathesis polymerization (REMP) to yield cyclic polyalkyne(s) and/or polyalkene(s).
Provided herein are compounds having a structure represented by formula (I), or dimers thereof:
Also provided herein are compounds having the structures:
Also provided herein are methods of preparing the compounds of formula (I), and dimers thereof, according to the disclosure, comprising:
Also provided herein is a cyclic polymer having a structure according to formula (V):
Also provided herein are methods of preparing cyclic polymers of formula V or VI, the method comprising: admixing a plurality alkene monomers, alkyne monomers, or both in the presence of the compounds of formula (I), or dimers thereof, of the disclosure under conditions sufficient to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer.
Provided herein are compounds having a structure represented by formulas (I), (II), (III), (IV), (V), and (VI), and methods of making and using said compounds. In embodiments, compounds having a structure represented by formulas (I) and (IV) can be in the form of a dimer. Compounds having a structure represented by formula (I), and dimers thereof, can be used as a catalyst in the preparation of cyclic polymers. Advantageously, compounds having a structure represented by formula (I), or dimers thereof, can generate high-molecular weight cyclic polyalkynes.
The compounds of the disclosure have structures represented by formulas (I), (II), (III), (IV), (V), and (VI) and these compounds may also be referred to as “compounds of formula (I),” “compounds of formula (II),” “compounds of formula (III)”, “compounds of formula (IV),” “compounds of formula (V),” and “compounds of formula (VI),” herein, respectively.
Modifications and other embodiments will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented herein and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims.
It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” can include the aspect of “consisting of.” Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.
As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.
As used herein, the term “alkyl” refers to straight chained and branched saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty two carbon atoms, or one to twenty carbon atoms, or one to ten carbon atoms. The term Cn means the alkyl group has “n” carbon atoms. For example, C4 alkyl refers to an alkyl group that has 4 carbon atoms. C1-20alkyl and C1-C20 alkyl refer to an alkyl group having a number of carbon atoms encompassing the entire range (i.e., 1 to 20 carbon atoms), as well as all subgroups (e.g., 1-20, 2-15, 1-10, 5-12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Nonlimiting examples of alkyl groups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. A specific substitution on an alkyl can be indicated by inclusion in the term, e.g., “haloalkyl” indicates an alkyl group substituted with one or more (e.g., one to 10) halogens.
As used herein, the term “heteroalkyl” is defined similarly as alkyl except that the straight chained and branched saturated hydrocarbon group contains, in the alkyl chain, one to five heteroatoms independently selected from oxygen (O), nitrogen (N), and sulfur(S). In particular, the term “heteroalkyl” refers to a saturated hydrocarbon containing one to twenty carbon atoms and one to five heteroatoms. In general, in embodiments wherein the heteroalkyl is provided as a substituent, the heteroalkyl is bound through a carbon atom, e.g., a heteroalkyl is distinct from an alkoxy or amino group.
As used herein, the term “cycloalkyl” refers to an aliphatic cyclic hydrocarbon group containing four to twenty carbon atoms, for example, four to fifteen carbon atoms, or four to ten carbon atoms (e.g., 4, 5, 6, 7, 8, 10, 12, 14, 15, 16, 17, 18, 19 or 20 carbon atoms). The term Cn means the cycloalkyl group has “n” carbon atoms. For example, C5 cycloalkyl refers to a cycloalkyl group that has 5 carbon atoms in the ring. C5-8 cycloalkyl and C5-C8 cycloalkyl refer to cycloalkyl groups having a number of carbon atoms encompassing the entire range (i.e., 5 to 8 carbon atoms), as well as all subgroups (e.g., 5-6, 6-8, 7-8, 5-7, 5, 6, 7, and 8 carbon atoms). Nonlimiting examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Unless otherwise indicated, a cycloalkyl group can be an unsubstituted cycloalkyl group or a substituted cycloalkyl group. The cycloalkyl groups described herein can be isolated or fused to another cycloalkyl group, a heterocycloalkyl group, an aryl group and/or a heteroaryl group, or a bicyclic group or a tricyclic group. For example, the cycloalkyl groups described herein can be a cyclohexyl fused to another cyclohexyl, or an adamantyl.
As used herein, the term “heterocycloalkyl” is defined similarly as cycloalkyl, except the ring contains one to five heteroatoms independently selected from oxygen, nitrogen, and sulfur. In particular, the term “heterocycloalkyl” refers to a ring containing a total of five to twenty atoms, for example three to fifteen atoms, or three to ten atoms, of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Nonlimiting examples of heterocycloalkyl groups include piperidine, tetrahydrofuran, tetrahydropyran, dihydrofuran, morpholine, and the like. The heterocycloalkyl groups described herein can be isolated or fused to another heterocycloalkyl group, a cycloalkyl group, an aryl group, and/or a heteroaryl group. In some embodiments, the heterocycloalkyl groups described herein comprise one oxygen ring atom (e.g., oxiranyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl).
As used herein, the term “alkenyl” is defined identically as “alkyl,” except for containing at least one carbon-carbon double bond, and having two to thirty carbon atoms, for example, two to twenty carbon atoms, or two to ten carbon atoms. The term Cn means the alkenyl group has “n” carbon atoms. For example, C4 alkenyl refers to an alkenyl group that has 4 carbon atoms. C2-7 alkenyl and C2-C7 alkenyl refer to an alkenyl group having a number of carbon atoms encompassing the entire range (i.e., 2 to 7 carbon atoms), as well as all subgroups (e.g., 2-6, 2-5, 3-6, 2, 3, 4, 5, 6, and 7 carbon atoms). Specifically contemplated alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, and butenyl. Unless otherwise indicated, an alkenyl group can be an unsubstituted alkenyl group or a substituted alkenyl group.
As used herein, the term “aryl” refers to monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) carbocyclic aromatic ring systems having six to twenty carbon atoms, for example six to fifteen carbon atoms or six to ten carbon atoms. The term Cn means the aryl ring structure has “n” carbon atoms and does not include carbons atoms in a substituent. For example, C6 aryl refers to an aryl group that has 6 carbon atoms in the ring. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unless otherwise indicated, an aryl group can be an unsubstituted aryl group or a substituted aryl group.
As used herein, the term “heteroaryl” refers to a cyclic aromatic ring system having five to twenty total ring atoms (e.g., a monocyclic aromatic ring with 5-6 total ring atoms), of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Unless otherwise indicated, a heteroaryl group can be unsubstituted or substituted with one or more, and in particular one to four, substituents selected from, for example, halo, alkyl, alkenyl, OCF3, NO2, CN, NC, OH, alkoxy, amino, CO2H, CO2alkyl, aryl, and heteroaryl. In some cases, the heteroaryl group is substituted with one or more of alkyl and alkoxy groups. Heteroaryl groups can be isolated (e.g., pyridyl) or fused to another heteroaryl group (e.g., purinyl), a cycloalkyl group (e.g., tetrahydroquinolinyl), a heterocycloalkyl group (e.g., dihydronaphthyridinyl), and/or an aryl group (e.g., benzothiazolyl and quinolyl). Examples of heteroaryl groups include, but are not limited to, thienyl, furyl, pyridyl, pyrrolyl, oxazolyl, quinolyl, thiophenyl, isoquinolyl, indolyl, triazinyl, triazolyl, isothiazolyl, isoxazolyl, imidazolyl, benzothiazolyl, pyrazinyl, pyrimidinyl, thiazolyl, and thiadiazolyl. When a heteroaryl group is fused to another heteroaryl group, then each ring can contain five to twenty total ring atoms and one to five heteroatoms in its aromatic ring.
As used herein, the term “hydroxy” or “hydroxyl” refers to the “—OH” group. As used herein, the term “thiol” refers to the “—SH” group.
As used herein, the term “alkoxy” or “alkoxyl” refers to a “—O-alkyl” group. As used herein, the term “aryloxy” or “aryloxyl” refers to a “—O-aryl” group. As used herein, the term “heteroaryloxy” or “heteroaryloxyl” refers to a “—O-heteroaryl” group.
As used herein, the term “alkylthio” refers to a “—S-alkyl” group. As used herein, the term “arylthio” refers to a “—S-aryl” group.
As used herein, the term “halo” is defined as fluoro, chloro, bromo, and iodo. The term “haloalkyl” refers to an alkyl group that is substituted with at least one halogen, and includes perhalogenated alkyl (i.e., all hydrogen atoms substituted with halogen), for example, CH3CHCl2, CH2ICHBr2CH3, or CF3.
As used herein, the term “oxo” refers to a ═O group.
As used herein, the term “amino” refers to a —NH2 group, wherein one or both hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, the term “amido” refers to an amino group that is substituted with a carbonyl moiety (e.g., —NRC(═O) or —C(═O)—NR), wherein R is a substituent on the nitrogen (e.g., alkyl or H). As used herein “imine” refers to a —N(R)═CR2 group, wherein each R is independently a H, alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. When referring to a ligand, the term “amine” refers to a —NH3 group, where one, two, or three hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. When referring to a ligand, the term “amide” refers to a NR2 group, wherein each R is independently a hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group.
As used herein, the term “phosphine” refers to a —PH3 group, wherein 0, 1, 2, or 3 hydrogens can be replaced with an alkyl, cycloalkyl, aryl group, heterocycloalkyl, or heteroaryl. As used herein “phosphite” refers to a —P(OR)3 group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, “phosphonite” refers to a —PR(OR)2 group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, “phosphinite” refers to a —PR2(OR) group, wherein each R can individually be alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, the term “diphosphine” refers to a —P(R2)—(CH2)n—P(R2)— group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group and n can be 1, 2, 3, 4, or 5.
As used herein, the term “carbene” refers to a —CH2 ligand, wherein 0, 1, or 2 hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group.
As used herein, the term “N-heterocyclic carbene” refers to a carbene, wherein the carbene is a ring atom in a heterocycle comprising 1 to 5 nitrogen atoms. Examples of N-heterocyclic carbenes include, but are not limited to,
wherein, each R group is independently selected from the group of: H, alkyl, cycloalkyl, alkenyl, aryl, alkoxy, aryloxy, heterocycloalkyl, and heteroaryl.
As used herein, the term “metallacycle” refers to a cycloalkyl or a heterocycloalkyl wherein one of the ring atoms is replaced by a metal atom.
As used herein, the term “substituted,” when used to modify a chemical functional group, refers to the replacement of at least one hydrogen radical on the functional group with a substituent. Substituents can include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, heterocycloalkyl, heterocycloalkenyl, ether, polyether, thioether, polythioether, aryl, heteroaryl, hydroxyl, oxy, alkoxy, heteroalkoxy, aryloxy, heteroaryloxy, ester, thioester, carboxy, cyano, nitro, amino, amido, acetamide, and halo (e.g., fluoro, chloro, bromo, or iodo). When a chemical functional group includes more than one substituent, the substituents can be bound to the same carbon atom or to two or more different carbon atoms.
As used herein, “bidentate ligand” refers to a ligand that has two atoms that can coordinate directly to the metal center of a metal complex, e.g., a single molecule which can form two bonds to a metal center. Non-limiting examples of bidentate ligands include ethylenediamine, bipyridine, phenanthroline, and diphosphine.
A “neutral ligand,” as used herein, refers to a ligand that, when provided as a free molecule, does not bear a charge. Examples of neutral ligands include, but are not limited to, water, phosphines, ethers (e.g., tetrahydrofuran), and amines (e.g., pyridine, triethylamine, or the like). An “anionic ligand” refers to a ligand that, when provided as a free molecule, has a formal charge of −1. Examples of anionic ligands include, but are not limited to, chloride, methoxy, ethoxy, ispropoxy, tertbutoxy, tertbutyl, neopentyl, triflate, and cyclopentadienyl.
Provided herein are compounds having a structure represented by formula (I) or dimers thereof:
In general, M is a transition metal. In embodiments, M is selected from chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), rhodium (Rh), iridium (Ir), and osmium (Os). In embodiments, M is Mo or W.
In general, Q is a neutral or anionic ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, Q is selected from S, O, N, NR5, N(R5)2, P(R6)2, C, CR7, C(R7)2, BR8, Si(R9)2, Se, and Te. In embodiments, Q is selected from S, O, N, NR5, P(R6)2, C, CR7, C(R7)2, and BR8. In some embodiments, Q is O, N, or NR5. In embodiments, M is Mo or W and Q is O, N, or NR5.
In general, X is selected from a bond, S, O, N, NR5, Se, Te, C1-C4haloalkyl, C1-C4alkyl, C2-C4alkenyl, C4-C10cycloalkyl, Ar1, C1-C4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X is selected from, C1-C4alkyl, O, NR5, C4-C10cycloalkyl, Ar1 or C1-C8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X is C1-C4alkyl,
In embodiments, M is Mo or W, Q is O, N, or NR5, and X is C1-C4alkyl,
In general, each R1 is independently selected from H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R1 together with the carbon atom to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R1 is independently selected from H, C1-C20alkyl, C1-C20haloalkyl, C4-C20cycloalkyl, or Ar1 or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one R1 is H, C1-C5haloalkyl, C1-C6alkyl or C4-C8cycloalkyl, or Ar1. In embodiments, each R1 is H, CH3, Ph, or CF3′ or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, at least one R1 is H, CH3, Ph, or CF3. In embodiments, each R1 is H.
In general, each R2 is independently selected from H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R2 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R2 is independently selected from H, C1-C20alkyl, C1-C20haloalkyl, C4-C20cycloalkyl, or Ar1. In embodiments, at least one R2 is H, C1-C5haloalkyl, C1-C6alkyl or C4-C5cycloalkyl, or Ar1. In embodiments, at least one R2 is H, CH3, Ph, or CF3. In embodiments, each R2 is H. In embodiments, each R2 is CH3. In embodiments, M is Mo or W, Q is O, N, or NR5, X is C1-C4alkyl,
and each R2 are H, CH3, Ph, or CF3.
In general, R3 is selected from a bond, —C(R1)2—, —C(R1)2C(R1)2—, —C(R1)2C(R1)2C(R1)2—, —C(R1)2C(R1)2C(R1)2C(R1)2—, and —C(R1)2C(R1)2C(R1)2C(R1)2C(R1)2—. In embodiments, R3 can be selected from —C(R1)2—, —C(R1)2C(R1)2—, —C(R1)2C(R1)2C(R1)2—, or —C(R1)2C(R1)2C(R1)2C(R1)2—. In embodiments, R3 is —C(R1)2— or —C(R1)2C(R1)2—. In embodiments, R3 is —C(R1)2, and two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, R3 is —C(R1)2, and two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, M is Mo or W, Q is O, N, or NR5, X is C1-C4alkyl,
each R2 are H, CH3, Ph, or CF3, R3 is —C(R1)2— or —C(R1)2C(R1)2—, and each R1 is H, CH3, Ph, or CF3′ or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S.
In general, L is a neutral or anionic ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, L comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.
In embodiments, L is an anionic ligand. In embodiments, L is selected from the group of N(R5)2, N(R5), OR10, SR11, O, S, OS(O2)CF3, carbene, N-heterocyclic carbene, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10 and R11 are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R5)2, N(R5), OR10, SR11, OS(O2)CF3, carbene, N-heterocyclic carbene, wherein each of R10 and R11 are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R5), OR10, OS(O2)CF3, carbene, and N-heterocyclic carbene, wherein R10 is selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1 and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R5), OS(O2)CF3, and OR10, wherein R10 is selected from C1-C22 alkyl and Ar1. In embodiments, L is selected from the group of N(R5), OS(O2)CF3, and OR10, wherein R10 is selected from tert-butyl, phenyl, and substituted phenyl and R5 is selected from Ar1 and C4-C8 cycloalkyl. In embodiments, L is N(R5) wherein R5 is selected from Ar1 and C4-C8 cycloalkyl. In embodiments, M is Mo or W, Q is O, N, or NR5, X is C1-C4alkyl,
each R2 are H, CH3, Ph, or CF3, R3 is —C(R1)2— or —C(R1)2C(R1)2—, each R1 is H, CH3, Ph, or CF3′ or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, and L is selected from the group of N(R5), OS(O2)CF3, and OR10, wherein R10 is selected from tert-butyl, phenyl, and substituted phenyl and R5 is selected from Ar1 and C4-C8 cycloalkyl.
In general, each L′ is independently absent or a neutral or anionic ligand. In embodiments, at least one L′ is a neutral ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, each L′ is independently absent or comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.
In embodiments, at least one L′ is an anionic ligand. In embodiments, each L′ is independently absent or selected from the group of N(R5)3, N(R5)2, N(R5), O(R10)2, OR10, S(R11)2, SR11, OS(O2)CF3, N-heterocyclic carbene, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C4-C8heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10 and R11 are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, each L′ is independently absent or selected from the group of N(R5)3, N(R5)2, O(R10)2, OR10, S(R11)2, SR11, OS(O2)CF3, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C4-C8heteroaryl, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10 and R11 are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1, C4-C8heteroaryl, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.
In embodiments, at least one L′ is independently selected from N(R5)3, N(R5)2, O(R10)2, OR10, N-heterocyclic carbene, or C1-C6 alkyl. In embodiments, at least one L′ is independently selected from Ar1, C4-C8heteroaryl, O(R10)2, OR10, or C1-C6 alkyl, wherein each of R10 is independently selected from C1-C22 alkyl, Ar1, or two R10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, at least one L′ is independently selected from pyridine, tetrahydrofuran, tert-butyl, or two L′ together form —OCH2CH2O—. In embodiments, M is Mo or W, Q is O, N, or NR5, X is C1-C4alkyl,
each R2 are H, CH3, Ph, or CF3, R3 is —C(R1)2— or —C(R1)2C(R1)2—, each R1 is H, CH3, Ph, or CF3′ or two vicinal R1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, L is selected from the group of N(R5), OS(O2)CF3, and OR10, wherein R10 is selected from tert-butyl, phenyl, and substituted phenyl and R5 is selected from Ar1 and C4-C8 cycloalkyl, and L′ are independently absent or selected from Ar1, C4-C8heteroaryl, O(R10)2, OR10, or C1-C6 alkyl, wherein each of R10 is independently selected from C1-C22 alkyl, Ar1, or two R10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.
The disclosure further provides compounds selected from the group of:
The compounds of the disclosure can be present as a monomer or a dimer. As used herein, the term “dimer(s)” refers to an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. The compounds of the disclosure can comprise homodimers, i.e. the dimer comprises two identical monomers. The compounds of the disclosure can comprise cyclic dimers, i.e. the dimer comprises two monomers connected through two or more sites on each monomer. Generally, the compounds of the disclosure can form dimers in solution; however, the compounds of the disclosure can also be present as monomers.
In various embodiments, the compound is a dimer. In some embodiments, the compound is a dimer having a structure represented by formula (I-dimer):
In various embodiments, the compound is a dimer with the structure:
The disclosure further provides methods of making the compound having a structure represented by formula (I), the method includes admixing a compound of formula (II) and a compound of formula (III) to form a compound of formula (IV) or dimer thereof, and admixing a compound of formula (IV), or dimer thereof with a deprotonating agent to form the compound of formula (I), or dimer thereof:
In general, La and Lb can be any ligand as defined herein for L. La and Lb can comprise one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl. La and Lb can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, La and Lb are the same.
In embodiments, La and/or Lb is an anionic ligand. In embodiments, La and/or Lb is selected from the group of N(R5a)2, N(R5a), OR10a, SR11a, O, S, OS(O2)CF3, carbene, N-heterocyclic carbene, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10a and R11a are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, La and/or Lb is selected from the group of N(R5a)2, N(R5a), OR10a, SR11a, OS(O2)CF3, carbene, N-heterocyclic carbene, wherein each of R10 and R11 are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, La and/or Lb is selected from the group of N(R5a), OR10a, OS(O2)CF3, carbene, and N-heterocyclic carbene, wherein R10a is selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, La and/or Lb is selected from the group of N(R5a), OS(O2)CF3, and OR10a, wherein R10a is selected from C1-C22 alkyl and Ar1a. In embodiments, La and/or Lb is selected from the group of N(R5a), OS(O2)CF3, and OR10a, wherein R10a is selected from tert-butyl, phenyl, and substituted phenyl and R5 is selected from Ar1a and C4-C8 cycloalkyl. In embodiments, La and/or Lb is N(R5a) wherein R5a is selected from Ar1a and C4-C8 cycloalkyl. Ar1a can be any Ar1 as defined herein. R5a can be any R5 as defined herein.
In general, L′a and L′b can be any ligand as defined herein for L′. When present, L′a and L′b can be neutral ligands or an anionic ligands. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and are described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, each L′a and L′b is independently absent or comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.
In embodiments, at least one L′a and L′b is an anionic ligand and at least one L′a and L′b is a neutral ligand. In embodiments, each L′a and/or L′b is independently absent or selected from the group of N(R5a)3, N(R5a)2, N(R5a), O(R10a)2, OR10a, S(R11a)2, SR11a, OS(O2)CF3, N-heterocyclic carbene, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10a and R11a are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, each L′a and/or L′b is independently absent or selected from the group of N(R5a)3, N(R5a)2, O(R10a)2, OR10a, S(R11a)2, SR11a, OS(O2)CF3, C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C4-C8heteroaryl, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R10a and R11a are independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C4-C8heteroaryl, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R10a together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.
In embodiments, at least one L′a and L′b is independently selected from N(R5a)3, N(R5a)2, O(R10a)2, OR10a, N-heterocyclic carbene, or C1-C6 alkyl. In embodiments, at least one L′a and/or L′b is independently selected from Ar1a, C4-C8heteroaryl, O(R10a)2, OR10a, or C1-C6 alkyl, wherein each of R10 is independently selected from C1-C22 alkyl, Ar1a, or two R10a together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, at least one L′a and/or L′b is independently selected from pyridine, tetrahydrofuran, tert-butyl, or two L′a and/or L′b together form —OCH2CH2O—. In embodiments, each L′b corresponds to (e.g., is the same as) an L′a.
In general, Qa and Qb can be any ligand as defined herein for Q. Qa and Qb can be neutral or anionic ligands. The neutral ligands of the disclosure can be L-type ligands as disclosed herein. Generally, Qa and Qb are selected from S, O, N, NR5a, N(R5a)2, P(R6a)2, C, CR7a, C(R7a)2, BR8a, Si(R9a)2, Se, and Te. In embodiments, Qa and Qb are selected from S, O, N, NR5a, P(R6a)2, C, CR7a, C(R7a)2, and BR8a. In embodiments, Qa and Qb are selected from O, N, or NR5a. In embodiments, Qa and Qb are the same. R6a, R7a, R8a, and R9a can be any R6, R7, R8, or R9 as defined herein, respectively.
In general, Xa and Xb are selected from a bond, S, O, N, NR5a, Se, Te, C1-C4haloalkyl, C1-C4alkyl, C2-C4alkenyl, C4-C10cycloalkyl, Ar1a, C1-C4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, Xa and Xb are selected from C1-C4alkyl, O, NR5a, C4-C10cycloalkyl, Ar1a, or C1-C8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, Xa and Xb are C1-C4alkyl,
In general, Z is selected from H, halo, or a counterion for Qa. In embodiments, Z is H or a counterion for Qa. In embodiments, Z is Li, Na, or K.
In general, each R1a and R1b can be any R1 as defined herein. R1a and R1b can be independently selected from H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R1a or R1b together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R1a or R1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.
In embodiments, each R1a and R1b is independently selected from H, C1-C20alkyl, C1-C20haloalkyl, C4-C20cycloalkyl, or Ar1a or two vicinal R1a or R1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one R1a and/or R1b is H, C1-C5haloalkyl, C1-C6alkyl or C4-C8cycloalkyl, or Ar1a. In embodiments, at least one R1a and/or R1b is H, C1-C5haloalkyl, C1-C6alkyl or C4-C8cycloalkyl, or Ar1a. In embodiments, each R1a and/or R1b is H, CH3, Ph, or CF3′ or two vicinal R1a or R1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, at least one R1a and/or R1b is H, CH3, Ph, or CF3. In embodiments, each R1a and/or R1b is H. In embodiments, each R1b corresponds to (e.g., is the same as) an R1a.
In general, each R2a and R2b can be any R2 as defined herein. R2a and R2b can be independently selected from H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R2a together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.
In embodiments, each R2a and/or R2b is independently selected from H, C1-C20alkyl, C1-C20haloalkyl, C4-C20cycloalkyl, or Ar1a. In embodiments, at least one R2a and/or R2b is H, C1-C5haloalkyl, C1-C6alkyl or C4-C8cycloalkyl, or Ar1a. In embodiments, at least one R2a and/or R2b is H, CH3, Ph, or CF3. In embodiments, each R2a and/or R2b is H. In embodiments, each R2a and/or R2b is CH3. In embodiments, each R2b corresponds to (e.g., is the same as) an R2a.
In general, R3a and R3b can be any R3 as defined herein. R3a and/or R3b can be selected from a bond, —C(R1a)2—, —C(R1a)2C(R1a)2—, —C(R1a)2C(R1a)2C(R1a)2—, —C(R1a)2C(R1a)2C(R1a)2C(R1a)2—, and —C(R1a)2C(R1a)2C(R1a)2C(R1a)2C(R1a)2—. In embodiments, R3a and/or R3b is —C(R1a)2—, —C(R1a)2C(R1a)2—, —C(R1a)2C(R1a)2C(R1a)2—, or —C(R1a)2C(R1a)2C(R1a)2C(R1a)2—. In embodiments, R3a and/or R3b is —C(R1a)2— or —C(R1a)2C(R1a)2—. In embodiments, R3a and/or R3b is —C(R1a)2, and two vicinal R1a together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, R3a and/or R3b is —C(R1)2, and two vicinal R1a together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, each R3b corresponds to (e.g., is the same as) an R3a.
In general, each R5a, R6a, R7a, R8a, and R9a can be any R5, R6, R7, R8, and R9 disclosed herein, respectively. In embodiments, each R5a, R6a, R7a, R8a, and R9a is independently selected from C1-C22 alkyl, C4-C8 cycloalkyl, Ar1a, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R5a, two vicinal R6a, two vicinal R7a, two vicinal R8a, or two vicinal R9a, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.
In general, M is a transition metal. In embodiments, M is selected from chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), rhodium (Rh), iridium (Ir), and osmium (Os). In embodiments, M is Mo or W.
In general, the deprotonating agent comprises an ylide, LiN(SiMe3)2, or KH. In embodiments, the deprotonating agent is Ph3P═CH2.
In general, the compound of formula (II) and the compound of formula (III) can be admixed under conditions sufficient to form a compound having a structure represented by formula (I) or dimer thereof. In embodiments, the admixing comprises a molar ratio of the compound of formula (II) and the compound of formula (III) of at least about 1:0.8, respectively. In embodiments, the admixing compromises the compound of formula (II) and the compound of formula (III) in a molar ratio of at least 1:0.8, or in a range of about 1:0.8 to about 1:1.5. In general, increasing the concentration of the compound of formula (II) can increase the rate the reaction to form the compound of formula (I) or dimer thereof; however, as the concentration of the compound of formula (III) increases, the likelihood of intermolecular reactions also increases, such as, the aggregation of multiple metal complexes, or over ligation of the metal center with the compound of formula (III).
In general, about one molar equivalent (e.g., at least 0.8 molar equivalents) of the compound of formula (III) per molar equivalent of the compound of formula (II) can be used to form the compound of formula (I) or dimer thereof.
In general, the compound of formula (IV) or dimer thereof and the deprotonating agent can be admixed under conditions sufficient to form the compound having a structure represented by formula (I), or dimer thereof. In embodiments, the admixing comprises a molar ratio of the compound of formula (IV) and the deprotonating agent of at least about 1:1, respectively. It will be understood that the molar ratio for admixing a compound of formula (IV) with the deprotonating agent refers to the molar ratio of the total monomers of formula (IV) (whether present as individual compounds or joined as a dimer) to the deprotonating agent. In embodiments, the admixing comprises the compound of formula (IV) and the deprotonating agent in a molar ratio of at least 1:1, or in a range of about 1:1 to about 1:10, or about 1:1 to about 1:5, or about 1:1 to about 1:3. In general, increasing the concentration of deprotonating agent can increase the rate the reaction to form the compound of formula (I); however, as the concentration of the deprotonating agent increases, the likelihood of intermolecular reactions also increases, such as, the aggregation of multiple metal complexes, or over ligation of the metal center with the deprotonating agent.
In general, about one molar equivalent (e.g., at least 1 molar equivalent) of the deprotonating agent per molar equivalent of the compound of formula (IV) can be used to form the compound of formula (I) or dimer thereof.
In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) or the compound of formula (IV) and the deprotonating agent can occur neat, for example, in cases where the compound of formula (II) or the compound of formula (III) or the compound of formula (IV) is a liquid. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) or the compound of formula (IV) and the deprotonating agent can occur in solution. Suitable solvents include but are not limited to, nonpolar aprotic solvents, such as, benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof.
In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) comprises a solvent. In refinements of the foregoing embodiments, the solvent comprises a nonpolar aprotic solvent. In further refinements of the foregoing embodiments, the nonpolar aprotic solvent comprises benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent comprises a solvent. In refinements of the foregoing embodiments, the solvent comprises a nonpolar aprotic solvent. In further refinements of the foregoing embodiments, the nonpolar aprotic solvent comprises benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof.
The admixing of the compound of formula (II) and the compound of formula (III), and the compound of formula (IV) and the deprotonating agent can occur at any suitable temperature for any suitable time. It is well understood in the art that the rate of a reaction during admixing can be controlled by tuning the temperature. Thus, in general, as the reaction temperature increases the reaction time can decrease.
Reaction temperatures can be in a range of about −80° C. to about 100° C., about −70° C. to about 80° C., about −50° C. to about 75° C., about −25° C. to about 50° C., about 0° C. to about 35° C., about 5° C. to about 30° C., about 10° C. to about 30° C., about 15° C. to about 25° C., about 20° C. to about 30° C., or about 20° C. to about 25° C., for example, about 0° C., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., or about 35° C. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) occurs at a temperature in a range of about 0° C. to about 35° C., or about 10° C. to about 30° C., or about 20° C. to about 30° C. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent occurs at a temperature in a range of about 0° C. to about 35° C., or about 10° C. to about 30° C., or about 20° C. to about 30° C.
Reaction times can be instantaneous or in a range of about 30 seconds to about 72 hours, about 1 minute to about 72 hours, about 5 minutes to about 72 hours, about 10 minutes to about 48 hours, about 15 minutes to about 24 hours, about 1 minute to about 24 hours, about 5 minutes to about 12 hours, about 10 minutes to about 6 hours, about 20 minutes to about 1 hour, about 20 minutes (min) to about 12 hours (h), about 25 min to about 6 h, or about 30 min to about 3 h, for example, about 30 seconds, 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 75 min, 90 min, 105 min, 2 h, 3 h, 4 h, 5 h, 6 h, 12 h, 18 h, 24 h, 36 h, 48 h, 60 h, or 72 h. When the reaction temperature increases above 100° C., generally the risk of decomposition of the product increases. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) occurs for a time in a range of about 1 minute to about 24 hours, or about 5 minutes to about 12 hours, or about 10 minutes to about 6 hours, or about 20minutes to about 1 hour. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent occurs for a time in a range of about 1 minute to about 24 hours, or about 5 minutes to about 12 hours, or about 10 minutes to about 6 hours, or about 20minutes to about 1 hour.
As demonstrated in the examples below, the compounds of formula (I) are dynamic in solution and generally have a dimer structure in the solid state.
The disclosure further provides a method of preparing a cyclic polymer, the method including admixing a plurality of alkene monomers, alkyne monomers, or both in the presence of the compound of formula (I) or dimer thereof, under conditions sufficient to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer.
Advantageously, compounds having a structure represented by formula (I), or dimers thereof, can generate high-molecular weight cyclic polymers.
Cyclic polymers can be prepared from any monomer that includes a carbon-carbon double bond or a carbon-carbon triple bond. In embodiments, the admixing comprises a plurality of alkyne monomers. In embodiments, the admixing comprises a plurality of alkene monomers.
Suitable alkyne monomers include, but are not limited to, C2-C20alkynes, C8-C20 monocyclic cycloalkynes, 8-20 membered monocyclic heterocycloalkynes comprising one to five ring heteroatoms selected from S, O, and N, C8-C20polycyclic cycloalkynes, or 8-20 membered polycyclic heterocycloalkynes comprising one or more ring heteroatoms selected from S, O, and N. The alkyne monomers can be substituted or unsubstituted. For example, the plurality of alkyne monomers can include cyclooctyne, cycloocta-1,5-diyne, phenylacetylene or
Suitable alkene monomers include, but are not limited to, C3-C20alkenes, C5-C20 monocyclic cycloalkenes, 5-20 membered monocyclic heterocycloalkenes comprising one to five ring heteroatoms selected from S, O, and N, C5-C20polycyclic cycloalkenes, or 5-20 membered polycyclic heterocycloalkenes comprising one or more ring heteroatoms selected from S, O, and N. The alkene monomers can be substituted or unsubstituted. For example, the plurality of alkene monomers can include norbornene or cyclooctene.
The polymerization reaction occurs upon combining in a fluid state the compound having a structure according to formula (I), or dimer thereof, and the plurality of alkenes, alkynes, or both. In some embodiments the reaction can be in neat alkene, alkyne, or both, wherein the monomers are provided in a fluid state. In some embodiments, the reaction can include a solvent such that the fluid state can be in solution.
Examples of solvents that may be used in the polymerization reaction include, but are not limited to, organic (e.g., nonpolar aprotic solvents) that are inert under the polymerization conditions, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, aliphatic hydrocarbons, or mixtures thereof. In embodiments, the solvent is a nonpolar aprotic solvent. In embodiments, the nonpolar aprotic solvent comprises benzene, toluene, deuterated analogs thereof, or combinations thereof.
The polymerization can be carried out at, for example, ambient temperatures (e.g., about 20° C. to about 25° C.) at dry conditions (e.g., about 0-1% RH) under an inert atmosphere (e.g., nitrogen or argon). Polymerization temperatures can be in a range of about 0° C. to about 35° C., about 10° C. to about 30° C., or about 20° C. to about 30° C. Reaction times can be instantaneous or otherwise until completion. The progress of the reaction can be monitored by standard techniques, e.g., nuclear magnetic resonance (NMR) spectroscopy. In embodiments, the reaction times are in a range of about 30 minutes to about 12 hours, about 1 hour to about 3 hours, about 1 hour to about 10 hours, about 1 hour to about 24 hours, or about 5 hours to about 24 hours. Polymerization times will vary, depending on the particular monomer and the metal complex. The rate of the reaction can decrease if the temperature of the polymerization is below room temperature. Reactions that occur over 100° C. can lead to the catalyst decomposing.
The method of preparing cyclic polymers includes the plurality of alkene monomers, alkyne monomers, or both, and the compound of formula (I), or dimer thereof, in a molar ratio in a range of about 1,000,000:1 to about 10:1, or about 100,000:1 to about 50:1, or about 50,000:1 to about 100:1, or about 50,000:1 to about 500:1, or about 50,000:1 to about 100:1, respectively. For example, the molar ratio of the plurality of alkene monomers, alkyne monomers, or both, to the compound of formula (I), or dimer thereof, is about 1,000,000:1, about 500,000:1, about 100,000:1, about 50,000:1, about 25,000:1, about 10,000:1, about 5,000:1, about 1000:1, about 500:1, or about 100:1.
Polymerization may be terminated at any time by addition of a solvent effective to precipitate the polymer, for example, methanol. The precipitated polymer may then be isolated by filtration or other conventional means.
The molecular weight of the cyclic polymers can be small, equivalent to oligomers of three to ten repeating units, or the molecular weights can be of any size up to tens and hundreds of thousands or millions in molecular weight, for example, in a range of about 200 Da to about 5,000,000 Da, about 500 Da to about 4,000,000 Da, about 1,000 Da to about 3,000,000 Da, about 5,000 Da to about 2,000,000 Da or about 10,000 Da to about 1,000,000 Da. The molecular weight is measured using gel permeation chromatography (GPC) and is calculated in number averaged molecular weight.
The disclosure further provides cyclic polymers, synthesized via the method above including admixing a plurality of alkene monomers, alkyne monomers, or both in the presence of the compound of formula (I), or dimer thereof, under conditions sufficient to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer, having a structure represented by formula (V) or formula (VI):
In general, the dashed line is optionally a double bond or a triple bond. In embodiments, the dashed line can be a double bond. In embodiments, the dashed line can be a triple bond.
In general, each R12 is independently absent, H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C1-C20alkoxy, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R12 is independently absent, H, C1-C20haloalkyl, C1-C20alkyl, C1-C20alkoxy, or C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R12 is independently absent, H, C1-C4haloalkyl, C1-C4alkyl, C1-C4alkoxy, or C1-C4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R12 is independently absent, H, C1-C4alkyl, or C1-C4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R12 is independently absent, H, CH3, or tert-butyl, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member aryl or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R12 is independently absent or H. In embodiments, each R12 is independently absent or H, or two vicinal R12 together with the carbon atoms to which they are attached, form a five- to eight-member aryl.
In general, each R13 is independently selected from H, C1-C20haloalkyl, C1-C20alkyl, C2-C20alkenyl, C4-C20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C1-C20alkoxy, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R13 is independently selected from, H, C1-C20alkyl, C4-C20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C1-C20alkoxy, C1-C20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C1-C20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R13 is independently selected from, H, C1-C15alkyl, C4-C20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C1-C15alkoxy, C1-C15heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C4-C15heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.
In general, n is an integer of at least 2. In embodiments, n can be in a range of about 2 to about 5,000,000, about 2 to about 1,000,000, about 2 to about 500,000, about 2 to about 100,000, about 2 to about 50,000, about 5 to about 100,000, about 10 to about 500,000, about 25 to about 250,000, or about 50 to about 50,000.
In embodiments, the cyclic polymer is a compound having the structure:
Benzene, hexanes, diethyl ether, tetrahydrofuran, pentane, and toluene were degassed, dried using a GlassContour drying column or equivalent, and stored over 3 Å molecular sieves prior to use. 1,2-benzenedimethanol was purchased from Oakwood Chemical and recrystallized from diethyl ether. W(CtBu)(CH2tBu)(O-2,6-iPr2C6H3) was prepared according to the method published in Tonzetich et. al, Organometallics 2007, 26, 475-477. All other chemicals were used without purification unless otherwise noted.
The overall scheme for the ligand synthesis is shown in
A 2-neck round bottom flask equipped with a stir bar, septum and stopcock flow adapter under argon was charged with 1,2-benzenedimethanol (7.654 g, 55.402 mmol) and 400 mL of dry dichloromethane. The mixture was stirred and cooled in an ice/water bath, 0° C. Through the septum, phosphorus tribromide (1.75 mL, 18.6 mmol) was added dropwise via syringe to the cold stirring solution. The reaction was stirred at 0° C. for 2 h then warmed naturally to ambient temperature while stirring for 1.5 h. The solution was filtered through silica and the volatiles were removed in vacuo. The products were separated via column chromatography (SiO2; hexanes/ethyl acetate 17:1). Upon solvent removal in vacuo 2-(bromomethyl)benzenemethanol was obtained.
1H NMR (300 MHz, C6D6): δ 7.15 (s, 1H, Ar—H), 6.99 (td, 1H, J=7.2, 1.9 Hz, Ar—H), 6.96-6.90 (m, 2H, Ar—H), 4.41 (d, 2H, J=5.7 Hz, HO—CH27), 4.17 (s, 2H, Br—CH28), 0.87 (d, 1H, J=5.8 Hz, OH).
13C NMR (101 MHz, C6D6): δ 140.0, 135.8, 130.7, 129.0, 128.6, 62.3, 31.0.
A dry round bottom flask equipped with a stir bar was charged with zinc bromide (0.059 g, 0.26 mmol), magnesium turnings (0.642 g. 26.4 mmol), dry diethyl ether (10 mL) and fitted with a dropping funnel containing a solution of 3-bromo-1-(trimethylsilyl)-1-propyne (2.511 g, 13.13 mmol) in diethyl ether (8 mL). The apparatus was attached to a Schlenk line under argon and the addition started at ambient temperature. Once an exothermic reaction was observed, the flask was chilled to 0° C. in an ice/water bath. Upon completion of the addition the reaction was stirred for 2 h at 0° C. The concentration was found to be 0.53 M via titration of a water quenched aliquot of the reaction mixture with 0.10 M HCl(aq) with bromomethyl blue as an indicator. The reaction mixture allowed to settle and the solution was cannula transferred into the next reaction step.
A Schlenk flask equipped with a stir bar was charged with 2-(bromomethyl)-benzenemethanol (0.862 g, 4.28 mmol) as prepared in Example 1, and 30 mL of dry diethyl ether. To the flask was attached an addition funnel and the apparatus was placed on a Schlenk line. The flask was chilled, stirring, in an ice/water bath, 0° C. The solution of the generated Grignard, (3-(trimethylsilyl)prop-2-yn-1-yl)magnesium bromide prepared in Example 2 was transferred to the addition funnel via cannula (approx. 18 mL, 0.72 M). The Grignard solution was added dropwise to the chilled flask with stirring. After the complete addition, the reaction flask was allowed to warm naturally to ambient temperature and stirred overnight (12 hours). Cool deionized (DI) water was added to quench the reaction, and additional ether was added to dilute the organic layer. The organic layer was washed with DI water, brine, and dried over magnesium sulfate. The ether was filtered and the solvent removed in vacuo. The products were separated via column chromatography (SiO2; hexanes/ethyl acetate 4:1).
1H NMR (300 MHz, C6D6): δ 7.20-7.17 (m, 1H, Ar—H), 7.09-7.04 (m, 2H, Ar—H), 7.02-6.99 (m, 1H, Ar—H), 4.32 (s, 2H, OH—CH27), 2.71 (t, 2H, J=7.4 Hz, CH28), 2.36 (t, 2H, J=7.4 Hz, CH29), 1.08 (s, 1H, OH), 0.18 (s, 9H, TMS).
13C NMR (101 MHz, C6D6): δ 139.3, 139.0, 129.9, 128.8, 127.9, 126.8, 107.4, 85.6, 63.1, 31.5, 22.1, 0.2.
In a round bottom flask equipped with a stir bar, 14 mL diethyl ether and (2-(4-(trimethylsilyl)but-3-yn-1-yl)phenyl)methanol (0.213 g, 0.916 mmol) as prepared in Example 3 were added. The solution was stirred and a 1.16 M solution of TBAF in THF (0.95 mL, 1.1 mmol) was added. The mixture quickly turned opaque with a yellow oil on the bottom of the flask and was left stirring overnight (12 hours). The mixture was diluted with ether, and then washed with 1.0 M HCl (20 mL) followed by deionized water and brine. The organic layer was dried over magnesium sulfate, filtered, and then solvents removed in vacuo.
1H NMR (600 MHz, C6D6): δ 7.19 (dd, J=6.9, 2.4 Hz, 1H, Ar—H), 7.09-7.02 (m, 2H, Ar—H), 6.97 (dd, J=7.0, 2.1 Hz, 1H, Ar—H), 4.29 (s, 2H, CH27), 2.67 (t, J=7.6 Hz, 2H, CH28), 2.25 (td, J=7.6, 2.6 Hz, 2H, CH29), 1.75 (t, J=2.7 Hz, 1H, CH11), 1.13 (s, 1H, OH).
13C NMR (101 MHz, C6D6): δ 139.2, 138.8, 129.6, 128.6, 128.0, 126.8, 84.0, 69.6, 63.0, 31.4, 20.4.
A round bottom flask equipped with a stir bar was charged with iodobenzene (1.132 g, 5.548 mmol), tetrakistriphenylphosphine palladium(0) (0.0644 g, 0.0557 mmol), copper (I) iodide (0.0211 g, 0.111 mmol), and triethylamine. The mixture was stirred under argon and the (2-(but-3-yn-1-yl)phenyl)methanol (0.8883 g, 5.544 mmol) from Example 4 was added. The opaque yellow mixture was stirred at ambient temperature overnight (12 h). Aqueous NH3/NH4Cl (60 mL) was added to quench the reaction and the mixture was extracted with diethyl ether. The ether was dried over sodium sulfate, filtered, and solvent removed in vacuo. The product was purified by column chromatography (SiO2; hexanes/ethyl acetate 4:1).
1H NMR (400 MHz, C6D6): δ 7.46 (m, 2H, Ar—H), 7.28-7.18 (m, 1H Ar—H), 7.13-6.73 (m, 5H Ar—H), 4.35 (d, J=5.7 Hz, 2H, CH27), 2.80 (t, J=7.5 Hz, 2H, CH28), 2.53 (t, J=7.5 Hz, 2H, CH29), 0.83 (t, J=5.7 Hz, 1H, OH).
13C NMR (101 MHz, C6D6): δ 139.3, 139.1, 129.8, 128.7, 128.6, 128.0, 127.9, 126.8, 124.6, 90.2, 82.1, 63.1, 31.7, 21.6.
A round bottom flask equipped with stir bar and pressure equalizing dropping funnel was charged with W(CtBu)(CH2tBu)(O-2,6-iPr2—C6H3)2 (0.208 g, 0.306 mmol) and 5 mL of benzene. A solution of the (2-(4-phenylbut-3-yn-1-yl)phenyl)methanol (0.072 g, 0.304 mmol) prepared in Example 5 in 5 mL benzene was added dropwise via addition funnel with stirring. After stirring for 18 h the volatiles were removed in vacuo. Pentane, 4 mL, was added to the resulting dark viscous residue. The resulting suspension was filtered, and the pale-yellow solid was washed three times with pentane and dried in vacuo. Crystals suitable for single-crystal x-ray analysis were obtained by dissolving the product in warm benzene leaving the solution to sit undisturbed.
1H NMR (400 MHz, C6D6): δ 7.71-7.63 (m, 1H), 7.32 (dd, J=7.8, 1.7 Hz, 1H), 7.20 (dd, J=7.5, 1.8 Hz, 1H), 7.07 (t, J=7.6 Hz, 1H), 7.02-6.89 (m, 2H), 6.86-6.68 (m, 3H), 6.09-5.84 (m, 3H), 3.88-3.84 (m, 1H), 3.70-3.61 (m, 1H), 3.58-3.37 (m, 2H), 3.20-3.07 (m, 1H), 2.14 (d, J=14.9 Hz, 1H), 2.08-2.03 (m, 1H), 1.90 (d, J=14.7 Hz, 1H), 1.69 (d, J=7.0 Hz, 3H), 1.64 (d, J=3.9 Hz, 2H), 1.58 (d, J=4.2 Hz, 1H), 1.51 (d, J=6.7 Hz, 3H), 1.36 (d, J=6.9 Hz, 4H), 1.27 (d, J=6.8 Hz, 3H), 1.07 (s, 9H).
1H13C gHSQC, gHMBC spectra (400 MHz, C6D6): δ 286.7, 165.0, 164.0, 142.2, 140.6, 136.2, 136.0, 132.4, 131.1, 130.0, 129.8, 128.7, 126.8, 123.0, 122.8, 85.9, 84.9, 79.1, 46.1, 36.6, 35.7, 35.2, 34.3, 33.7, 33.5, 27.5, 26.5, 26.3, 24.9, 24.8, 24.6, 24.4, 21.5, 20.5 132.6, 130.2, 128.8, 126.9, 122.8, 122.5, 86. 78.8, 46.1, 36.7, 36.6, 34.2, 33.5, 27.5.
The 1-D NOESY/EXSY (500 MHz, toluene-d8) spectrum is shown in
In a nitrogen atmosphere glovebox, a scintillation vial equipped with a stir bar was charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (0.040 g, 0.069 mmol) and 2.0 mL of dry toluene. To this solution was added, in one portion, 0.40 mL of a 3.45 mM toluene stock solution of W(CCH2CH2C6H4-o-CH2O)(CHtBu)(O-2,6-iPr2—C6H3) as prepared in Example 6, with stirring. After 27 m, 2.0 mL of dry toluene were added and the polymer was precipitated in 15 mL methanol with stirring. The polymer was isolated via filtration and washed with additional methanol and dried.
1H NMR (500 MHz, CDCl3): δ 7.40 (d, J=8.4 Hz, 2H), 6.69 (d, J=2.7 Hz, 2H), 6.64 (dd, J=8.4, 2.6 Hz, 2H), 3.71 (t, J=6.5 Hz, 4H), 3.21 (s, 4H), 1.60-1.70 (m, 4H), 1.15-1.45 (m, 36H), 0.87 (t, J=7.0 Hz, 6H).
Stacked 1H NMR (C6D6, 500 MHz, 25° C.) spectra are shown in
In a nitrogen atmosphere glovebox, scintillation vials equipped with stir bars were charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (15 mg, 0.026 mmol) and 1.0 mL of dry toluene. To these solutions, 100.0 μL of a 5.18 mM toluene stock solution of W(CCH2CH2C6H4-o-CH2O)(CHtBu)(O-2,6-iPr2—C6H3) as prepared in Example 6, was added in one portion with stirring. The vials were sealed and mixed. After the appropriate reaction time, the vials were removed from the glovebox, unsealed and quenched with methanol, 10-12 mL. The polymers were isolated via filtration, washed with additional methanol and dried overnight under vacuum.
The experiment was performed in two separate runs; entries 1-4 were performed in one run while entries 5-9 were performed separately. Reaction times and yields are listed in Table 1.
aTime reported in minutes.
bDetermined from isolated yield.
Thus, Example 8 demonstrates general preparation conditions for preparing a cyclic polymer according to the disclosure. The catalysts and polymers of the disclosure are further characterized in Example 9.
Additionally, the polymerization of 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen was investigated with commercially-available W(CCMe3)(OCMe3)3, following a similar procedure as Example 8.
In a nitrogen atmosphere glovebox, a scintillation vial equipped with a stir bar was charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (15 mg, 0.026 mmol) and 1.0 mL of dry toluene. To this solution 100.0 μL of a 5.29 mM toluene stock solution of W(CCMe3)(OCMe3)3 was added in one portion with stirring. The vial was sealed and mixed. The vial was removed from the glovebox, unsealed and quenched by adding methanol, 10-12 mL after 5 minutes. The polymer was isolated via filtration, washed with additional methanol and dried overnight under vacuum. The results from the W(CCMe3)(OCMe3)3 compound (I-PoPE) were compared with the results obtained for catalysts of the disclosure, (c-PoPE) and are presented in Table 2.
aMinutes,
bDetermined (g/mol) by size-exclusion chromatography (SEC) equipped with differential refractive index (DRI) and viscometry using dichlorobenzene (DCB) as the mobile phase at 140° C.
cLinear generated using W(CCME3)(OCMe3)3.
d% conversion of 3,8-didocdecyloxy-5,6-dihydro-11,12-didehydrodibonzo[a,e]-[8]annulen.
Solution properties of cyclic poly-(o-phenylene ethynylene) were compared with those of linear poly-(o-phenylene ethynylene) via GPC analysis, providing evidence on the polymer cyclic topology. With a smaller hydrodynamic volume, cyclic polymers are expected to elute later than their linear counterparts, for a given molecular weight. As shown in the plot of log MW versus elution volume (
Formation of cyclic poly-(o-phenylene ethynylene) was confirmed by analyzing the intrinsic viscosity of the prepared poly-(o-phenylene ethynylene) in THF using a viscometer-equipped GPC. Due to their smaller overall dimensions, cyclic polymers are expected to exhibit lower intrinsic viscosity compared with analogous linear polymers for a given molecular weight. As shown in the Mark-Houwink-Sakurada plots in
Additionally, as shown in the plots of mean square radius of gyration (<Rg2>) versus molar mass (
However, one entry from both runs of Example 8 (c-PoPE-1 and c-PoPE-7) are outliers that do not follow the trend. In the case of these polymers, the generated poly-(o-phenylene ethynylene) had greater intrinsic viscosity than the linear analogue, as shown on the Mark-Houwink-Sakurada plots (
Thus, Example 9 demonstrates preparation of cyclic polymers using a catalyst of the disclosure and linear polymers using a catalyst not of the disclosure.
This application claims the priority benefit under 35 U.S.C. § 119 (e) of U.S. Provisional Application No. 63/244,319, filed Sep. 15, 2021, the entire disclosure of which is incorporated herein by reference.
This invention was made with government support under Grant Number 1856674, awarded by the National Science Foundation. The government has certain rights in the invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US22/43643 | 9/15/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63244319 | Sep 2021 | US |
