A crystalline porous metal-organic framework material, a method for synthesizing said material and applications for its use

Abstract

The present invention relates to a method for synthesizing crystalline porous metal-organic frameworks (MOFs), comprising mixing the following components at suitable conditions, including a suitable temperature and duration, in the presence of a suitable solvent: a metal cation, such as zirconium; a phenolic linker molecule comprising catechol and / or gallol moieties, such as ellagate and / or ellagic acid; and a cationic template, comprising at least 5 non-hydrogen atoms; thereby obtaining the MOF material. In further aspects, the invention also relates to crystalline porous metal-organic frameworks (MOFs) as synthesized by the method of the disclosure, and MOFs wherein the cationic template has been replaced with another cationic species, as well as uses of the MOFs for various applications, such as target molecule capture.

Description

[0001]A crystalline porous metal-organic framework material, a method for synthesizing said material and applica^ons for its use TechnicalfieldThe present inven^on is in thefield of materials chemistry. More specifically, the present inven^onrelates to a novel family of metal-organic frameworks (MOFs), including a method of synthesising the MOFs, various uses and applica^ons of the novel MOFs, as well as new materials comprising the MOFs. Technical background Metal-organic frameworks (MOFs) are a class of porous crystalline materials made of metal ca^ons linked by organic “linker” ligand molecules that are assembled as well-defined framework structures.These materials are a^rac^ve for their diverse chemical composi^ons, high surface areas, and tunablestructures and proper^es. MOFs have been inves^gated for a range of applica^ons. However, for manyapplica^ons, more aptly tailored MOF structures than those presently known are required. Due to thediverse chemical composi^ons and structures of MOFs, their proper^es can vastly differ, including theirstability and performance, as well as environmental and biological compa^bility.The majority of MOFs are charge-neutral frameworks made by self-assembly without any form oftemplate that guides the shape of the porous structure. A small number of reports have demonstratedthat different structures of anionic MOFs can be made using the same combina^on of metal ca^on andorganic linker by introducing ca^onic template molecules, such as various amines [Fang et al. Cryst.Growth Des.2008, 8, 1, 319–329].Over the last decade the zirconium-based UiO-66 has been u^lized as an archetypal MOF. This form ofZr-MOF has been studied together with amine templates by, among others, Long et. al. (2012), DMelloet. al (2019) and Pourmadadi et. al. (2022), of which Long et. al. (2012) and DMello et. al (2019)explored the poten^al for MOF-based photocatalysts, while Pourmadadi et. al. (2022) looked at fabrica^on techniques of UiO-66 for diagnos^c procedures. Similarly, Mohyuddi et. al., (2019) has alsodisclosed a method for the synthesis of gallic acid modified UiO-66 to be used as a biomarker in earlydiagnosis of disease. However, while this has the poten^al to develop many new framework materialswith similar chemical composi^ons, fully replacing these ca^onic templates in previous examples andaccessing the pores of these MOFs has remained a challenge due to either the collapse of the porousMOF material a^er removal of the template, or difficul^es in removing the template altogether. Also,the majority of MOFs are made using synthe^c organic linkers, o^en bearing carboxylate, azolate orpyridine func^onal groups.Incorpora^on of the naturally occurring molecule ellagic acid into chemically robust MOF materials hasrecently been realized (Svensson Grape et al., 2020, Svensson Grape et al., 2023). These previouslypublished materials comprised of metal ca^ons and ellagate anions were made using only water andace^c acid as solvents, as is the case for the bismuth ellagate SU-101 (Svensson Grape et al., 2020), orthrough the addi^on of simple basic solvents such as ammonia or dimethylformamide, as is the casefor the zirconium ellagate SU-102 (Svensson Grape et al., 2023). During synthesis at 120°C, ammoniaand N,N-dimethylformamide form the ca^ons ammonium and dimethylammonium, respec^vely,which have 1 and 3 non-hydrogen atoms, respec^vely, that reside in the pores of the MOF, yielding aniden^cal framework structure independent of which ca^on present during the synthesis. Hence, theporous material obtained does not exhibit any structural diversity. However, these organic amines arerela^vely small molecules with simple molecular structures.Therefore, there remains a strive for novel MOFs with altered structures for improved proper^es, aswell as an improved process for synthesizing MOFs.SummarySurprisingly, the present inventors have now succeeded in providing larger and more complex ca^onicspecies, such as other amines or ammonium species, by u^lizing high amine concentra^ons and higherreac^on temperatures than what is required for SU-102, such as 160°C, that allows for a templa^ngeffect that can result in the forma^on of MOFs with dras^cally different structures, pore shapes,densi^es, symmetries,flexible / rigid behavior, stability, interpenetra^on, and / or complexity, whichcould in turn aid in the desire to improve the biological and environmental compa^bility of the material,and improve proper^es such as surface area, hydrophobicity / hydrophilicity, op^miza^on of the pore size and shape for targeted guest species, introduce binding sites for targeted guest molecules, or induce cataly^c ac^vity.Thus, the present inventors have succeeded in providing novel MOFs that are stable, have replaceabletemplates, and are of a higher complexity than those previously known. The novel MOFs have beenprepared by a novel synthesis method, according to this disclosure. Thus, according to afirst aspect there is provided a method for synthesizing crystalline porous metal-organic frameworks (MOFs), comprising mixing the following components at suitable condi^ons,including a suitable temperature and dura^on, in the presence of a suitable solvent: (a) a metal ca^on, such as zirconium;(b) a phenolic linker molecule comprising catechol and / or gallol moie^es, such as ellagateand / or ellagic acid; and (c) a ca^onic template comprising at least 5 non-hydrogen atoms;thereby obtaining the MOF material. Hence, the present inventors have focused on developing a general method of synthesising MOFs thatare of a higher structural complexity and diversity, by employing templa^ng molecules withconsiderable size to direct the forma^on of unique structures compared to what was previously known.The selec^on of sufficiently large and complex ca^onic templates, in contrast to previous art, led to thediscovery of a number of new MOF structures and the realiza^on of the structure direc^ng role of theamine / ammonium or pyridine / pyridinium template species. The method as disclosed can be used tosynthesise MOFs when employing sufficiently large or complicated templates, resul^ng in a change inpore size and shape to maximize intermolecular interac^ons with the template, also affec^ngframework symmetry, structuralflexibility / rigidity, stability, interpenetra^on, and / or complexity of thematerial structures, which in turn could aid in the desire to improve the bio- and environmentalcompa^bility of the material and improve their proper^es for the desired applica^ons. This opens thepossibility to create many other new MOF materials with the same framework building units—a metalca^on and an organic linker molecule—by introducing a different templa^ng ion while keeping othersynthesis parameters constant.In some embodiments, the method further comprises the use of the following components andcondi^ons: (a) a zirconyl chloride octahydrate compound or salt, chosen from zirconyl chlorideoctahydrate and zirconium tetrachloride;(b) ellagic acid; and / or(c) the ca^onic template comprising at least 5 non-hydrogen atoms is chosen from amine,ammonium, phosphonium, sulfonium, thiazolium, pyridinium, piperidinium, pyrazolium, imidazolium, alkyl, aryl and ca^onic metal complexes. In some embodiments, the MOF syntheses is performed in the presence of water and / or ace^c acid, at a temperature of about 140-180^C, such as about 160^C, at a dura^on of about 1 hour.In some embodiments, (a) the ca^onic template is added in a concentra^on of (a) at least about 0,01ml template per ml solvent (water and / or ace^c acid), or at least about 0,03 ml template per ml solvent,or at least about 0,06 ml template per ml solvent, or at least about 0,1 ml template per ml solvent, orat least about 0,3 ml template per ml solvent, or at least about 0,6 ml template per ml solvent, or atleast about 1 ml template per ml solvent and / or (b) the ca^onic template is added in a concentra^onof (b) at least about 0,1 g template per 32 mg metal ca^on, such as Zr, or at least about 0,5 g templateper 32 mg metal ca^on, such as Zr, or at least about 1,0 g template per 32 mg metal ca^on, such as Zr,or at least about 5,0 g template per 32 mg metal ca^on, such as Zr and / or (c) the ca^onic template isadded in a molar ra^o of at least 0,5 – 2,0 mmol phenolic linker, such as ellagic acid, per 1 mmol metalca^on, such as Zr. Hereby, using these components and condi^ons the method can be used to synthesize MOFs in accordance with the present disclosure. Varia^ons of these composi^ons and condi^ons are alsoincluded, as long as the method works. For example, other sources of metal ca^ons (includingzirconium) are possible, as well as use of lower temperatures, such as room temperature, during thereac^on, e.g. by using more basic condi^ons. Typically, the MOFs of this disclosure were synthesizedusing 32 mg ZrOCl2, 60 mg ellagic acid, 2.5 mL H2O, 1mL ace^c acid, and anywhere from 0.1 - 1.0 g (orml) template, which would correlate to a range of (a) 0,02-0,30 g (or ml) template per ml solvent, (b)0,1 – 1,0 g (or ml) template per 32 mg metal ca^on such as Zr. However, broader ranges of theseconcentra^ons and molar ra^os are also included in the context of the present disclosure. According to some embodiments, the ca^onic template, in a subsequent step, is replaced, such as byion exchange, with another ca^onic species, such as an organic ca^on, a metal ca^on or a metalcomplex, for subsequent use to capture a target molecule.Typically, the anionic framework will strongly a^ract the guest ca^on (the other ca^onic species), andtherefore it will not easily be washed out. The selec^on of the ca^onic template thus enables the development of MOFs with an ideal pore structure for a specific target molecule. The replacement of the template allows for an op^mized crystal structure for capturing a target molecule or a moleculewith similar structural features to the target molecule, within the pores. Thus, this opens for a broadapplicability of the method and the resul^ng MOFs, wherein the MOFs can be designed to capture desired target molecules in various uses, such as pharmaceu^cal compounds, heavy metals, pollutants, catalysts, among others. Highly efficient and selec^ve capture of target chemicals is expected as a result of providing the method and the MOF materials of this disclosure. According to a second aspect, there is provided a crystalline porous metal-organic framework (MOF)material having the general formula Rz[M(HxP)YLW], wherein R is a ca^onic template comprising at least5 non-hydrogen atoms; M is a metal ca^on; HxP = phenolic linker molecule comprising catechol and / orgallol moie^es; L = addi^onal ligand; Z = 0,5-4; Y= 1-3; X = 0-4; W = 0-1.The synthesis of the crystalline porous MOF materials enables access to a diverse range of structurescompared to what was previously known. The crystalline porous MOF materials have an alteredstructure and thus can be made to suit a large number of applica^ons due to their improved proper^essuch as surface area, hydrophobicity / hydrophilicity, op^miza^on of the pore size and shape fortargeted replacement species, introduce binding sites for targeted replacement molecules, or to inducecataly^c ac^vity. Further, since the ca^onic template comprises at leastfive (5) non-hydrogen atoms, asuitably large size of the pore structure of the MOF is obtained. Moreover, using a high concentra^onof a template with 5 or more non-hydrogen atoms typically results in MOFs with structures thatconform to the shape of the templates.According to some embodiments, the MOF material has pore sizes in the interval from about 0.1 to 1.5nm (i.e. about 1 to 15 Å).The resul^ng pore sizes of the MOF materials have a direct effect on which target molecules may beadsorbed into the crystalline porous MOF material. In some embodiments, the pore size of the crystalline porous MOF material allows for larger molecules to be captured within the pores, thereby allowing the MOF materials to be used for a wide range of applica^ons. According to some embodiments, the metal ca^on is chosen from the group consis^ng of Zr(IV), Hf(V), Ti(IV) and Ce(IV). Hereby, the metal ca^on component can be varied in order to provide a large variety of poten^al MOFstructures. For example, ca^ons of Ce and Ti are o^en used for cataly^c applica^ons. Hf ca^onstypically makes as stable materials as those made from Zr ca^ons.According to some embodiments, the phenolic linker is a synthe^c or naturally occurring molecule chosen from ellagate, ellagic acid, rufigallol and other anthraquinone based catecholates and gallates, 5,5’-(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triol) and organic linkers with two or morecatecholate or gallate groups, such as 3,3ʹ,4,4ʹ,5,5ʹ-hexahydroxybiphenyl.In the porous crystalline MOF materials, the metal ca^ons are linked by phenolic “linker” ligand molecules leading to an assembled well-defined framework structure. The phenolic linker requires a total charge adapted to promote the forma^on of ca^onic frameworks. In some embodiments the charge is due to the rela^vely many anionic sites in the form of deprotonated phenolate groups. In other embodiments the linkers may alterna^vely be neutral ligands or ligands with fewer anionic sites.In some embodiments the phenolic linker is fully protonated ellagic acid (H4EA).The ellagate organic linker has rela^vely many anionic sites in the form of deprotonated phenolate groups, which o^en leads to an excess of nega^ve charge, thus resul^ng in anionic MOF frameworks. Thus, in order to promote the forma^on of neutral or ca^onic MOF frameworks, neutral ligands such as pyridines, or ligands with fewer anionic sites, such as carboxylates, imidazolates, phosphonates, sulfonates may be be^er suited. According to some embodiments, the ca^onic template comprising at least 5-nonhydrogen atoms has one or more of the following features: (i) the at least 5-non-hydrogen atoms are chosen from C, N, O, S, P, halogens, metal ca^ons; (ii) the at least 5 non-hydrogen atoms comprise at least one heteroatom (not H or C),such as O, N, S or P, or a metal ion; (iii) the template is an organic molecule, a halocarbon or a metal complex; (iv) the template has a molecular weight (Mw) in the interval of about 74 g / mol andabout 500 g / mol, such as in the interval of 74 g / mol and 350 g / mol;(v) the template comprises a primary, secondary, ter^ary and / or quaternary amine;(vi) the template comprises a primary amine being a di-amine or polyamine; (vii) the template comprises a molecular species bearing mul^ple func^onal groups having the ability to be ca^onic or become ca^onic under suitable condi^ons. Hereby, a large varia^on of template molecules are usable in the context of the present inven^on. C, N, O are typically the most common choices of non-hydrogen atoms in a template to be used in thepresent inven^on, and S or P atoms would be common for organic templates. Also, halocarbons withhalogens can be used as templates, and metal complexes comprising essen^ally any stable metal ca^oncan also be used. Further, bulky template molecules are typically preferred for forming MOFs having amore complex form. Thus, in some embodiments the template comprises a secondary, ter^ary orquaternary amine rather than a primary amine. In some embodiments, when using a primary amine,it may be advantageous to use a diamine or polyamine. In embodiments it may also be comprised of amolecular species bearing mul^ple func^onal groups that may be ca^onic or become ca^onic undercertain condi^ons. Moreover, in some embodiments, the ca^onic template comprising at least 5-non-hydrogen atoms comprises at least one heteroatom (atom not being carbon (C) or hydrogen (H)), such as nitrogen (N), sulfur (S) or phosphorus (P), or a metal ca^on (if a metal complex is used). Thus, out of the at leastfive (5) non-hydrogen atoms of the template, at least one (1) may be a heteroatom or metal ion. Further, with regard to molecular weight, heavier or much heavier templates may also be used,such as when using a heavy metal in a metal complex as template, or using an organic molecule withseveral heavy heteroatoms, like bromine. In embodiments, the minimum molecular volume of thetemplate comprisingfive non-H atoms is about 0.08 nm3.According to some embodiments, the ca^onic template is chosen from organic ca^ons, metal ca^onsand metal-organic ca^ons, including various nitrogen-based organic ca^ons, such as ammonium,pyridinium, piperidinium, pyrrolidinium, imidazolium and pyrazolium ca^ons; phosphorus-basedca^ons such as various phosphonium ca^ons; sulfur-based ca^ons such as sulfonium and thiazoliumcompounds; and metal-organic ca^ons such as metal complexes and target molecules to be used foradsorp^on. Hereby, the template is designed to be readily replicable with a large range of ca^ons. The choice of ca^onic template enables op^miza^on of the pore size and shape for targeted guest species. As disclosed, the crystalline porous MOF material have a wide range of poten^al templates.According to some embodiments, the ca^onic template is chosen from the group comprising N,N-dibutylformamide (DBF), Trihexylamine (THA), Diisobutylamine (DiBA), Hexamethylenediamine (HDA),1,4-Diazabicyclo[2.2.2]octane (DABCO), 4-tert-Butylaniline (tBAn), Tributylamine (TBA), Trioctylamine (TOA), Tetramethylammonium hydroxide (TMAOH), 2-Methylpentamethylenediamine (MPDA); Py = Pyridine, Bpy = 4,4’-Bipyridine, DMAP = 4-Dimethylaminopyridine, Ade = Adenine, DiPEA = Diisopropylethylamine, DMBPy = 5,5’-dimethyl-2,2’-bipyridine, Quin = quinine, PPA = p- phenylenediamine. Other templates according to the discussion and disclosure herein are also included in the scope of the inven^on. According to some embodiments, the MOF material is chosen from the group consis^ng of: SU-103 (HDBA)2[Zr(HxEA)2] HDBA = dibutylammoniumSU-104 (HTHA)2[Zr(HxEA)2] HTHA = trihexyammoinumSU-105 (HDiBA)2[Zr(HxEA)2] HDiBA = diisobutylammoniumSU-106 (H2DAH)[Zr(HxEA)2] H2HDA = hexamethylenediammoniumSU-107 (HDABCO)2[Zr(HxEA)2] HDABCO = 1,4-diazabicyclo[2.2.2]octaniumSU-108 (HtBAn)2[Zr(HxEA)2] HtBAn = 4-tert-butylaniliniumSU-109 (HTBA)2[Zr(HxEA)2] HTBA = tributylammoniumSU-110 (HTOA)2[Zr(HxEA)2] HTOA = trioctylammoniumSU-111 (HTMA)2[Zr(HxEA)2] HTMA = TetramethylammoniumSU-112 (H2MPDA)1[Zr(HxEA)2]H2MPDA =2- methylpentamethylenediammonium SU-113 (HPy)2[Zr(HxEA)2.5(OAc)] HPy = pyridiniumSU-114 (HBPy)2[Zr(HxEA)2] HBPy = 4,4’-bipyridinium monoca^onSU-115 (HDMAP)1-3[Zr(HxEA)2(OAc)] HDMAP = 4-dimethylaminopyridiniumSU-116 (HAde)1-3[Zr(HxEA)2] HAde = adeniniumSU-117 (HDiPEA)2[Zr(HxEA)2] HDiPEA = diisopropylethylammoniumSU-118 (HDABCO)3[Zr(HxEA)3] HDABCO = 1,4-diazabicyclo[2.2.2]octaniumSU-119 (HDMBPy)1-3[Zr(HxEA)2(DMBPy)] HDMBPy = 5,5’-dimethyl-2,2’-bipyridiniumSU-120 (HQuin)2[Zr(HxEA)2] HQuin = quininiumSU-121 (HPPA)2[Zr(HxEA)2.5(OAc)] HPPA = p-phenylenediaminiumSU-122 (HPPA)1-3Zr(HxEA)2] HPPA = p-phenylenediaminiumAccording to a third aspect, the present disclosure relates to a crystalline porous metal-organicframework (MOF) material having the general formula Rz[M(HxP)YLW], wherein R is a ca^onic species, which species has replaced a ca^onic template used for synthesizing the MOF material; M = metal ca^on, such as Zr; HxP = phenolic linker molecule comprising catechol or gallol moie^es; L = addi^onalligand such as acetate (OAc) or 2,2’-bipyridine; Z = 0,5-4; Y = 1-; X = 0-4; W = 0-1.Hence, a MOF wherein the original template used for synthesizing the MOF has been exchanged for aca^onic species is provided, which is useful for a variety of applica^ons. In some embodiments, the phenolic linker molecule is ellagate and / or ellagic acid, such as fully protonated ellagic acid (H4EA). In some embodiments, the ca^onic species is chosen from an organic ca^on, a metal ca^on, a metal complex, or ca^onic part of a larger molecule, such as a target molecule.In some embodiments, when Z = 0, the MOF material is essen^ally neutral. Hence, when Z = 0, no guestca^on or template is present in the MOF structure, which typically requires that the MOF structure is neutrally charged. In order to obtain only empty space with no guest ca^ons in the pores the MOF would need to be neutral, which can be done by making some of the phenolate groups on the ellagic acid to be protonated to reduce the total number of nega^ve charges on the framework. In some embodiments, the MOF material comprises an addi^onal ligand, such as an acetate, hydroxyl, pyridyl or carboxylate ligand. According to some embodiments, the crystalline porous metal-organic framework (MOF) materialaccording to the second and third aspect of the present disclosure is produced by the method accordingto thefirst aspect. According to some embodiments, the crystalline porous metal-organic framework (MOF) material according to the second and third aspect of the present disclosure is provided or supplied in the form of a powder, a pellet, or a powder or pellet inside a cartridge. According to some embodiments, the crystalline porous metal-organic framework (MOF) material according to the second and third aspect of the present disclosure exhibits at least one property transferred from the ca^onic template, wherein the property is chosen from any of the following: hydrophobicity, hydrophilicity, cataly^c ac^vity,fluorescence, phosphorescence, absorbance, acidity, basicity as well as adsorbent proper^es, including the selec^ve binding of certain guest species.According to some embodiments, the crystalline porous metal-organic framework (MOF) material isfor use in (i) removal of pollutants, heavy metals and / or other chemicals, such as pharmaceu^calmolecules, in an air or waterfilters, (ii) in drug delivery), or (iii) in heterogenous catalysis. According to a further aspect, there is provided a use of the crystalline porous metal-organic framework (MOF) material in removal of pollutants and / or other chemicals, such as pharmaceu^cal molecules, in an air or waterfilter. The various applica^ons of the MOF materials result from one of the main advantages of the present disclosure, i.e., that the use of suitable template guide the shape of the pore structure of the resul^ngMOF material, so that a molecule of interest or a molecule of similar shape and size as a molecule ofinterest, such as a pollutant or other target, can be used as templates, producing a porous materialthat is par^cularly well-suited for interac^ng with that specific molecule or molecules similar in shapeand size either in whole or in part. This approach further enables a wide range of larger molecules,including pollutants and / or other chemicals, such as pharmaceu^cal molecules to be captured in the pores of the framework and thus be removed from the environment. The applica^on is further madepossible by the improved bio- and environmental compa^bility of the materials from theirflexibility / rigidity, stability, interpenetra^on, and / or complexity of the structures. According to a further aspect, there is provided a use of the crystalline porous metal-organic framework (MOF) material in drug delivery. With theflexibility / rigidity, stability, interpenetra^on, and / or complexity of the structures of the MOFmaterials, their bio- and environmental compa^bili^es are such making them suitable for drug deliveryapplica^ons. According to a further aspect, there is provided a use of the crystalline porous metal-organic framework (MOF) material in heterogenous catalysis.The templates used for the synthesis of SU-103 to SU-122 are sufficiently large and complex molecules.In comparison, the prior art (SU-102) indiscriminately uses one of a variety of simple smallamine / ammonium species (i.e. ammonium, dimethylammonium, and diethylammonium) for thesynthesis of SU-102. For the prior art, these reagents were used as solvents and / or bases todeprotonate the reagent ellagic acid. In the present inven^on, inten^onally selec^ng larger and morecomplex amine / ammonium species resulted in the discovery of the new structures SU-103 to SU-112 and the realiza^on of the structure direc^ng role of the amine / ammonium species. This opens thepossibility to create many other new MOF materials with the same framework building units: a metalca^on and an organic linker molecule. Thus, having a sufficiently high concentra^on of a sufficientlylarge template molecule is one key to making the new templated MOFs.Effects and features of the various aspects are to a large extent analogous to those described above in connec^on with thefirst aspect. Embodiments men^oned in rela^on to thefirst aspect are largely compa^ble with the other aspects. The present disclosure will become apparent from the detailed descrip^on given below. The detailed descrip^on and specific examples disclose preferred embodiments of the disclosure by way of illustra^on only. Those skilled in the art understand from the guidance in the detailed descrip^on that changes and modifica^ons may be made within the scope of the disclosure. Hence, it is to be understood that the herein disclosed disclosure is not limited to the par^cular component parts of the kit described or steps of the methods described since such kit and method may vary. It is also to be understood that the terminology used herein is for the purpose of describing par^cular embodiments only, and is not intended to be limi^ng. It should be noted that, as used in the specifica^on and the appended claim, the ar^cles "a", "an", "the", and "said" are intended to mean that there are one or more of the elements unless the context explicitly dictates otherwise. Thus, for example, reference to "a part or "the part" may include several elements, and the like. Furthermore, the words "comprising", "including", "containing" and similar wordings do not exclude other elements or steps. Brief descrip^on of the drawingsFigure 1 discloses (Top) a general method for the synthesis of amine / ammonium-templated zirconiumellagate MOFs. (Bo^om) Amines and pyridines used for the synthesis of SU-103 – SU-122. Otherca^onic molecules and metal complexes can be used to develop other new MOFs. During MOFsynthesis, all of these amines protonate and become ca^onic ammonium species. N,N-dibutylformamide (DBF), which is used to make SU-103 (depicted), converts to dibutylammonium(DBA) during synthesis, and so DBA is also suspected to be able to form SU-103 as well.Figure 2 discloses crystal structures of amine- or pyridine-templated zirconium ellagate MOFs SU-103– SU-122. SU-102, the structure of which has been published, is also shown for comparison, wassynthesized using N,N-dimethylformamide (DMF) in the solvent mixture.Figure 3 discloses X-ray powder diffrac^on pa^erns of SU-103 to SU-122. Peaks from impurity phasesare marked with an *. The SU-118 structure was made as a minor phase together with SU-107, and therefore no powder pa^ern was provided. Detailed descrip^onThe present disclosure includes, in afirst aspect, a general synthesis method that was systema^callyapplied to discover a family of new MOFs, and could be further u^lized to discover many more newmaterials (Figure 1). Also included, in a second aspect, are a series of 20 new crystalline porous MOFmaterials denoted SU-103 – SU-122 (Figure 2) which were synthesized from the described synthesismethod. In a third aspect, the ca^onic template used for synthesizing the MOF materials of the second aspect has been replaced with another ca^onic species, opening up for a wide range of applica^ons.These new MOFs will be u^lized, according to further aspects, in uses including (i) capturing pollutantssuch as pharmaceu^cal compounds and heavy metals, among others, in air or waterfilters, (ii) in drugdelivery, and (iii) heterogenous catalysis.The 20 new materials are anionic MOFs made of metal ca^ons, such as zirconium(IV) (“Zr”) ca^ons,and phenolic linkers, such as ellagate linkers (derived from ellagic acid which can be extracted fromplant-based materials such as fruit peels and tree bark). Each of these 20 materials are made using adifferent amine / ammonium or pyridine / pyridinium-based ca^onic molecule (i.e. templates) having atleast 5-nonhydrogen atoms, which resides in the pores of the anionic MOF. Once the MOFs have formed, these templates can then be replaced for other ca^onic species such as metal ions (e.g. Na+),which can improve the bio- and environmental compa^bility of the material, and improve proper^essuch as surface area, hydrophobicity / hydrophilicity, introduce binding sites for targeted guest molecules, or induce cataly^c ac^vity. Either before or a^er the template has been replaced, the MOF can be applied to capture various guest species such as pollutants, catalysts, pharmaceu^cals, etc. As ca^onic species, to replace the template, e.g., the following can be used: essen^ally every metal ca^on could work as long as the metal ca^on is present in high enough concentra^on. For example, this includes Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Fe3+, Ni2+, Cu2+, Zn2+, Pb2+. In addi^on, other cataly^cally ac^ve metal ions such as Pd2+can be used. For environmental applica^ons, environmentally compa^ble metal ions such as Na+, K+, Mg2+, Ca2+, etc can be used, and other ions canbe used for applica^ons like catalysis or CO2 capture. The metal ca^on can e.g., be added as a salt, e.g.LiCl, NaCl, KCl etc.The inventors have used different templates to develop these new MOF materials. However, theyenvision that MOFs with op^mal pore shapes for capturing targeted chemicals can be achieved by ra^onally selec^ng the template. For example, in order to develop a MOF with an op^mized crystal structure for capturing a specific pharmaceu^cal pollutant, that pollutant molecule, or a molecule withsimilar structural features to the pollutant molecule, could be used as the template to form the MOFwith the ideal pore structure. The template would then be removed by e.g., ion exchange to free spacein the pores before the MOF is applied to then capture the target pollutant from a mixture such aspolluted water. This has not previously been reported for MOFs. This can be envisioned especially forpharmaceu^cal targets containing a ca^onic func^onal group, as well as other ca^onic pollutants. Forexample, atenolol and citalopram are examples of such environmentally concerning pharmaceu^calpollutants that have ca^onic ammonium groups at near neutral pH encountered in prac^cally relevantcondi^ons.In some embodiments, proper^es of the template molecules can also be transferred to the specificMOF formed. For example a hydrophobic template like trioctylamine, can result in the forma^on of a hydrophobic MOF (SU-110). One addi^onal example is to use afluorescent molecule as a template to introducefluorescent proper^es to the MOF, which is made in SU-120 with quinine, being afluorescent molecule, as a template. Other examples include using a template with Lewis or Bronsted acid or basesites, to introduce acidity or basicity. S^ll further, the inventors have discovered that the MOFs thatwere made with hydrophobic templates, are hydrophobic MOF crystals themselves. Thus, theproper^es of the MOF crystals can be changed by use of various templates with different chemical andphysical proper^es. Typically, it is required that the template molecule is kept in the MOF structure forthe property to be transferred and exhibited. In some embodiments, the property is chosen from anyof the following: hydrophobicity, hydrophilicity, cataly^c ac^vity,fluorescence, phosphorescence, absorbance, acidity, basicity as well as adsorbent proper^es, including the selec^ve binding of certain guest species.In some embodiments, the synthesis method can also be expanded to develop MOFs with differentchemical composi^ons. Other templates such as other amines, or non-nitrogen-based templates, suchas phosphorus or sulfur-based organic molecules, other ca^onic organic molecules, or ca^onic metalcomplexes could be used to develop other new MOFs. Zirconium(IV) could be replaced by other metalions including but not limited to hafnium(IV). The ellagic acid reagent (which deprotonates during forma^on of the MOF to form ellagate anions) can be replaced by other phenolic organic molecules bearing catechol and gallol moie^es.The synthesis method described offers a highly efficient way to discover many new MOFs with the sameframework composi^on (in this case zirconium ellagates). The principles could also be expanded for other metal ca^ons. Other phenolic organic linkers besides ellagate could also be used to develop otherfamilies of metal-phenolic frameworks. Also, the concept of using targeted species as templates for thedevelopment of MOFs has not been described before and can be used for the development of morera^onally designed MOFs with op^mal pore shapes for the capture of targeted chemicals. This methodand these materials can be used for highly efficient and selec^ve capture of target chemicals.Synthesis of the materialsThe materials described in this applica^on are all metal-organic frameworks (MOFs) — a class of porousmaterials prepared by combining metal ca^ons or metal ca^on clusters with organic “linker” molecules,forming extended coordina^on networks with high porosity. Typically, these materials are acquired as fine micro- / nanocrystalline powders that have pores on a molecular size scale (in the 10-10to 10-9mrange). The specific MOFs described in this disclosure are a novel family of MOFs made by combiningmetal ca^ons with phenolic linker molecules, in the presence of a template, also known as a structure- direc^ng agent (SDA). The described synthesis method allows for the forma^on of numerous anionic MOF materials with dis^nct framework structures, while using the same type of metal ca^on and organic linker but altering the ca^onic template. The materials in ques^on can be obtained in a range of synthesis condi^ons from mixtures typicallycomposed of a zirconium salt, ellagic acid, water and solvents, as well as an SDA that resides in thepores of the obtained framework material. The necessary components independent of what material is being targeted are (1) a metal ion source, such as a zirconium source, (2) a phenolic linker, such asellagic acid, and (3) a templa^ng ca^on, comprised offive or more non-hydrogen atoms, as those arethe molecular building blocks that make up all of the novel materials. Further varia^ons are possible in order to obtain other novel materials. Previously published materials comprised of metal ca^ons and ellagate anions were made using either no SDA with only water and ace^c acid as solvents, as is thecase for the bismuth ellagate SU-101 (Grape et al., 2020), or through the addi^on of a simple basicsolvent such as ammonium (one non-hydrogen atom), dimethylammonium (three non-hydrogenatoms, which can be derived from dimethylformamide), or diethylammonium (five non-hydrogenatoms ca^ons), as is the case for the zirconium ellagate SU-102, for which no structural diversity wasobserved despite varying the iden^ty of the small ca^onic species (Grape et al., 2023).The molecular templates evaluated so far to develop the novel MOFs are bulkier and more complicatedprimary, secondary, ter^ary, and quaternary amines or pyridine-based molecules bearing one or morenitrogen-based func^onal groups. During synthesis these amines and pyridines protonate and convertinto ammonium and pyridinium ca^ons respec^vely. Alterna^vely, the ammonium or pyridiniumca^ons could directly be used as reagents. The variety of templates could be expanded to use otherca^ons such as phosphonium, metal complexes, or even inorganic / organic pollutants of interest. Synthesis condi^onsThe aforemen^oned use of molecular templates represents one main difference between the materialsdescribed herein and those that have been published previously. Specifically, one unique aspect is theuse of templa^ng molecules for designing materials with pores of a specific shape and size. The nature of the pores in these materials greatly affects their performance in applica^ons related to their porousnature. This effec^vely permits a “lock-in-key” approach, where molecules of interest, e.g. a pollutantor substrate, or molecules of similar shape and size as a molecule of interest can be used as templates, producing a porous material that is par^cularly well-suited for interac^ng with that specific moleculeor molecules similar in shape and size either in whole or in part.While maintaining the same composi^on and overall structure of a material, many synthesis parameters can affect performance. Varying parameters such as temperature, ^me, pH, concentra^on of reagents, solvents, or the use of non-templa^ng addi^ves (such as so-called ‘modulators’), may result in different external / internal surface proper^es and different crystallite sizes. Both of these are aspects that affect proper^es such as adsorp^on capacity and adsorp^on kine^cs, among others. The preferred synthesis condi^ons include hydrothermal / solvothermal condi^ons of high temperatureand high pressure in a sealed container under autogenous pressure. Yet employing the same synthesiscondi^ons apart from the increased temperature also affords the materials, only requiring a longer synthesis ^me. The solvent used in the synthesis is preferably deionized water or a combina^on of deionized waterand ace^c acid in a suitable ra^o, such as 5:2, although other ra^os may also be used.A^er synthesis, the MOFs can be separated into solid powder, which typically is done by centrifuga^on. Also, a washing step with water and / or other suitable solvent can be included. Therea^er, the synthesized MOFs are typically dried a^er synthesis to remove solvent and / or other liquid. Typically, this drying process Is performed in an oven, even though other alterna^ves areconceivable. Without drying, the samples will be wet and it might be difficult to use them forapplica^ons such as gas adsorp^on. The samples could be dried at room temperature, which however would take more ^me than oven-drying. Also drying in an oven removes solvent such as water which can be trapped in the pores. Post-synthe^cally, the templates in the MOFs can then be replaced by ion exchange with a vast variety other ca^onic species including organic ca^ons, metal ca^ons, and metal complexes. Metal ca^ons Varia^ons of the templated MOFs include analogous isostructural MOFs with other ca^ons replacing Zr(IV). Metal ions known to adopt similar coordina^on environments and similar MOF structures as Zr-MOFs include Hf(IV), Ti(IV), Ce(IV) and Ln(III). These metals and other metals and / or metal ions may beused to dope the material including but not limited to transi^on metals and lanthanides. Phenolic linkers Varia^ons of the templated MOFs include analogous isostructural MOFs with other phenolic linker molecules replacing ellagate anions. These include organic linkers with two or more catecholate orgallate groups. These organic linker molecules can either be synthe^c or natural products. For example,the phenolic linker can be chosen from rufigallol and other anthraquinone based catecholates and gallates, 5,5’-(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triol), among other synthe^c and naturally occurring molecules with two or more catechol or gallol func^onal groups such as 3,3ʹ,4,4ʹ,5,5ʹ- hexahydroxybiphenyl.Ca^onic templatesVaria^ons of the ca^onic templates include organic ca^ons, metal ca^ons and metal-organic ca^ons.Organic nitrogen-based ca^ons include various alkyl and aryl ammonium, pyridinium, piperidinium,pyrrolidinium, imidazolium and pyrazolium ca^ons; phosphorus-based ca^ons such as variousphosphonium ca^ons; sulfur-based compounds such as sulfonium, and thiazolium ca^ons; and metal-organic ca^ons such as metal complexes.Synthesizing novel materials using non-nitrogen based compoundsThe inventors have primarily synthesized the MOFs of this disclosure using nitrogen-based organicca^ons as templates but other organic ca^ons and metal-organic ca^ons could also be used asstructure direc^ng agents. Examples of other organic ca^ons include phosphorus-based phosphonium ca^ons of the general formula PR4+(where R is a hydrogen, alkyl, aryl or halide group) or sulphur-based ca^ons such as sulfonium ca^ons of the general formula SR3+. Metal-organic ca^ons based on metalcomplexes are also an^cipated to func^on as structure direc^ng agents. Examples include but are notlimited to metal complexes made of various metals (e.g. Ni(II), Co(III), Fe(III), and many others) combined with ligands (including but not limited to amines, pyridines, etc.). An example of such a metal complex could be [Ni(en)3]2+(where en = ethylenediamine). Tailoring the template to develop new MOFsPrimarily, the templated MOFs that have been developed have been based on the use of complexca^onic templates that, when of a sufficient size, guide the forma^on of anionic MOF frameworks.The templates used for the synthesis of SU-103 to SU-122 are rela^vely large and complex molecules.In comparison, prior art (SU-102), indiscriminately uses one of a variety of small and simpleamine / ammonium species (i.e. ammonium, dimethylammonium, and diethylammonium), and no structure-direc^ng role could be iden^fied from the previous art. However, as described herein, inten^onally selec^ng larger and more complex amine / ammonium species in sufficiently highconcentra^ons resulted in the discovery of the new structures SU-103 to SU-122 and the realiza^on ofthe structure direc^ng role of the sufficiently large ca^onic species, in this case bearing ammoniumand pyridinium mo^fs. For example, introducing the template to the synthesis mixture in highconcentra^ons (e.g. >0.1 g amine per 32mg ZrOCl2) while maintaining a reac^on temperature of 160°C,resulted in new structures. This opens the possibility to create many other new MOF materials with the same framework building units: metal ca^on and organic linker molecule. Thus, in some embodiments, the ca^onic template is added in a concentra^on of at least about 0,1 gtemplate per 32 mg metal ca^on, such as Zr, or at least about 0,5 g template per 32 mg metal ca^on,such as Zr, or at least about 1,0 g template per 32 mg metal ca^on, such as Zr. The template can be asdefined elsewhere in this disclosure, such as an amine. The present inventors have also discovered that the concentra^on of the ca^onic template can be usedto control the synthesis process. For example, using 0,1-0,5 g of the ca^onic template DABCO forsynthesis results in forma^on of the prior art compound SU-102, whereas using 1,0 g DABCO forms SU-107 (other condi^ons the same).Post-synthe^c ca^on exchange Whichever ca^on occupies the pores of the as-synthesized material can be readily exchanged byimmersing the material in a 1 molar solu^on of a new ca^on in water. The concentra^on requireddepends both on the ca^onic species that is to be put into the MOF, as well as the ca^onic template. Hence, required concentra^on will vary, and the higher the concentra^on, the more likely ion exchange will be successful. Typically, 1 molar is sufficiently high. Thus, replacing the template is typically aprocess comprising s^rring the MOF loaded with the template in an aqueous solu^on of a salt (e.g.NaCl) containing the ca^on to be implemented (Na+). The concentra^on of the salt solu^on that needsto be used primarily depends on the nature of the pore where the template originally was located, andthus varies. However, with high enough concentra^ons, the inventors have found out that almost anyca^on thatfits in the pores can be forced in. See Example 6 for further details of a ca^on exchangeprocedure. Addi^onal coordina^ng group In some embodiments of the present disclosure, in addi^on to the phenolic linker, such as ellagic acid,coordina^ng to the metal ca^on, such as Zr, an addi^onal chemical coordina^ng group (an addi^onal ligand), such as an acetate group, is also coordina^ng. In some embodiments, this addi^onal ligand iseasily replaced by another molecule, such as a hydroxide, carboxylate, or a pyridyl ligand. Especially,this has been observed when preparing compounds SU-113, SU-115, SU-119 and SU-121. In someembodiments, a lower concentra^on of template (compare SU-121 with SU-122) results in anaddi^onal ligand (such as acetate) being part of the MOF.Applica^ons for useThe materials described in this inven^on could be used in various applica^ons, such as (i) in water orairfilters to remove pollutants and other chemical species, (ii) for drug delivery, (iii) for heterogeneouscatalysis. The synthesis method can easily be applied to discover many new MOF materials.Furthermore, the new MOFs are configured to obtain the desired selec^ve adsorp^on proper^es, i.e.,capturing the target pollutants rather than other chemical species in contaminated waters that mightbe less harmful to the environment.The MOF materials produced can be provided and sold / supplied e.g. in powder form or as a pellet.Alterna^vely, the MOF materials can be provided and sold / supplied as a powder or pellet inside acartridge, suitable for the specific need or applica^on. The inven^on will now be described with reference to the following examples, which are intended to exemplify the inven^on, without limi^ng its scope as defined by the appended claims. ExamplesSynthesis of the twenty (20) novel zirconium ellagate MOF materials have been successful and thecrystal structures of these 20 MOFs have been determined by the inventors. Preliminary results on several of the new MOFs have indicated good stability of the MOFs a^er ion exchange of the amines with smaller metal ca^ons such as Na+and Cs+.Example 1 - synthesis condi^onsTable 1 below lists the general synthesis condi^ons that have resulted in the novel MOFs. All MOFs can be prepared following the same general procedure (Table 1) by only changing the chemical species ofthe template (Table 2). The synthesis condi^ons can be extended to cover a range of temperatures,reagent concentra^ons, solvents, and addi^ves. The crucial part is the presence of a metal salt (typicallyzirconyl chloride octahydrate or zirconium tetrachloride), ellagic acid, and a molecular template. In atypical synthesis, reagents, solvents, and a polytetrafluoroethylene-coated (PTFE) s^r bar were added to a 5 ml pressure-resistant glass tubefi^ed with a polybutylene terephthalate cap bearing a PTFE lining. Thefilled and sealed glass tube was then put into a preheated aluminum block and heated at 160 °C for 1 hour while s^rring. The solid content of the tube was then recovered by centrifuging at6000 × g for 10 min. The obtained solid was then dried at 80 °C overnight in air. Alternate synthesisapproaches for obtaining the same materials can be envisioned, including the aforemen^oned variables, but also the overall synthesis approach and the synthesis container. Table 1. General synthesis condi^ons and the amounts of reagents used to synthesize all different MOF materials. Ellagic Zirconyl acid chloride Template Solvents Temperature (g) (ml) (°C) Time (h) 60 32 0,1 - 1 2.5 H2O 160 1 + 1 ace^c acidExample 2 – sources of templateTable 2. Reagents used as the source of the template. Note that all primary, secondary, and ter^ary amines protonate during synthesis, becoming ammonium ca^ons that reside in the pores of the MOFs. MOF Template reagent*1Template in as-synthesized MOF SU-103 N,N-dibutylformamide*2 (DBF) Dibutylammonium (DBA)SU-104 Trihexylamine (THA) Trihexyammonium (HTHA) SU-105 Diisobutylamine (DiBA) Diisobutylammonium (HDiBA) SU-106 Hexamethylenediammonium Hexamethylenediamine (HDA) (H2HDA) Tributylamine (TBA) Tributylammonium (HTBA)(TOA) (HTOA)SU-111 Tetramethylammonium hydroxide (TMAOH) Tetramethylammonium (TMA) 2-Methylpentamethylenediamine (MPDA) SU-113 Pyridinium (HPy)SU-114 4,4’-Bipyridine (BPy) 4,4’-Bipyridinium monoca^on (HBpy) SU-115 4-Dimethylaminopyridinium (HDMAP) 4-Dimethylaminopyridine (DMAP) Adenine (Ade) Adeninium (HAde) Diisopropyethylamine (DiPEA) Diisopropyethylammonium (HDiPEA)SU-118 1,4-Diazabicyclo[2.2.2]octane (DABCO) (HDABCO)SU-119 5,5’-Dimethyl-2,2’-bipyridinium (DMBPy) 5,5’-Dimethyl-2,2’-bipyridinium(HDMBPy) p-Phenylenediamine (PPA) p-Phenylenediaminium (HPPA)*1During synthesis all SDA which are not already ca^onic become and then remain protonated. *2N,N-dibutylformamide converts into dibutylammonium during MOF synthesis. *3 The template in SU-112 may be mono- or biprotonated, i.e., both HMPDA and H2MPDA may occur.Example–3 - Diffrac^on pa^ernsFigure 3 shows X-ray powder diffrac^on pa^erns of SU-103 to SU-122. These may be used foriden^fica^on of these novel phases, as well as an indica^on of their crystallinity, purity, and uniquestructures. Peaks from impurity phases are marked with an *. Thus, the X-ray powder pa^erns are likefingerprints of different crystalline materials. Each structure has a unique powder pa^ern. Example 4 - Topological informa^onThe IBU is the inorganic part of the structure. In some cases, the Zr is coordinated by 7 oxygen atoms (ZrO7) and other cases eight (ZrO8). In one case there are dimers of Zr2O12. The topology describes how the IBUs connect to one another. The space group describes the symmetry of the crystal and the unit cell parameters describe the size and shape of the repeat unit (the unit cell) of the crystal structure. See e.g., “h^ps: / / en.wikipedia.org / wiki / Crystal_structure” for more details on defining parameters. Table 3. Structural descriptors such as crystallographic details, topology, and the local inorganic building unit of the MOFs SU-103 to SU-122.MOF IBU*1 Net*2 SpaceUnit cell parameters groupa / Å b / Å c / Å α / ° β / ° γ / °SU-103 Zr2O12 pcu P-1 12.68 14.25 16.36 104.76 99.75 93.19SU-104 ZrO7 hcb P-1 15.31 17.04 20.37 96.49 113.26 102.38SU-105 ZrO8 dia C2 / m 26.80 25.43 13.69 90 115.59 90SU-106 ZrO8 dia-c*3 Fddd 25.28 26.32 35.70 90 90 90SU-107 ZrO7 pts P-1 8.91 19.30 20.56 67.83 89.78 85.21SU-108 ZrO7 hcb P21 / n 9.90 36.07 19.26 90 93.815 90SU-109 ZrO7 dia P-1 12.55 17.79 18.42 84.31 76.34 72.83SU-110 ZrO7 hcb P-1 16.15 19.21 20.11 77.32 86.75 74.36SU-111 ZrO7 hcb C2 / c 41.03 12.93 22.75 90 101.62 90SU-112 ZrO8 dia-c I-4c2 16 16 37 90 90 90SU-113 ZrO8 2c1 P21 / n 12.95 20.97 15.17 90 90.18 90SU-114 ZrO8 dia-c P2 / n 9.42 14.94 16.49 90 94.35 90SU-115 ZrO8 2c1 P-1 11.04 12.09 15.72 81.3 83.0 70.85SU-116 ZrO7 dia P-1 7.82 16.36 19.35 72.70 90.23 87.2SU-117 Zr2O12 pcu P21 / n 13.25 20.73 16.30 90 105.71 90SU-118 ZrO7 2c1 P-1 8.13 20.2 21.14 62.0 81.1 80.8SU-119 ZrO6N 2 hcb P-1 12.45 13.08 15.50 81.9 67.6 88.11SU-120 ZrO8 dia C2 15.78 35.57 14.55 90 109.96 90SU-121 ZrO8 2c1 P-1 11.77 13.09 13.69 103.75 106.12 96.6SU-122 ZrO8 dia-c C2 / c 25.54 20.65 20.56 90 122.76 90 Example 5 – Chemical formula and templates of synthesized MOFsTable 4. Chemical formula and templates of SU-103 to SU-112. MOF Chemical Formula TemplateSU-103 (HDBA)2[Zr(HxEA)2] HDBA = dibutylammoniumSU-104 (HTHA)2[Zr(HxEA)2] HTHA = trihexyammoinumSU-105 (HDiBA)2[Zr(HxEA)2] HDiBA = diisobutylammoniumSU-106 (H2DAH)[Zr(HxEA)2] H2HDA = hexamethylenediammoniumSU-107 (HDABCO)2[Zr(HxEA)2] HDABCOSU-108 (HtBAn)2[Zr(HxEA)2] HtBAn = 4-tert-butylaniliniumSU-109 (HTBA)2[Zr(HxEA)2] HTBA = tributylammoniumSU-110 (HTOA)2[Zr(HxEA)2] HTOA = trioctylammoniumSU-111 (HTMA)2[Zr(HxEA)2] HTMA = TetramethylammoniumSU-112 (H2MPDA)1[Zr(HxEA)2]H2MPDA = 2- methylpentamethylenediammonium SU-113 (HPy)2[Zr(HxEA)2.5(OAc)] HPy = pyridiniumSU-114 (HBPy)2[Zr(HxEA)2] HBPy = 4,4’-bipyridinium monoca^onSU-115 (HDMAP)1[Zr(HxEA)2(OAc)] HDMAP = 4-dimethylaminopyridiniumSU-116 (HAde)3[Zr(HxEA)2] HAde = adeniniumSU-117 (HDiPEA)2[Zr(HxEA)2] HDiPEA = diisopropylethylammonium(HDABCO)3[Zr(H EA) ]HDABCO = 1,4- SU-118 x 3diazabicyclo[2.2.2]octanium 5,5’-dimethyl-2,2’- bipyridinium SU-120 (HQuin)2[Zr(HxEA)2] HQuin = quininiumSU-121 (HPPA)2[Zr(HxEA)2.5(OAc)] HPPA = p-phenylenediaminiumSU-122 (HPPA)2[Zr(HxEA)2] HPPA = p-phenylenediaminiumGeneral formula of all the new MOFs: Rz[M(HxP)YLW].R is the ammonium or pyridinium template comprising at leastfive more carbon atoms, and W = 0-1,X = 1, Y=2 and Z=0,5-4 in these examples but can poten^ally vary in other MOFs.The difference in synthesis condi^ons between SU-121 and SU-122 is that in SU-1210.3g amine is used while for SU-1220.7g amine is used.For SU-115, SU-116, SU-119 and SU-122, Z may vary in the interval of 1-3.Example 6 – Replacing the template using ion-exchangeFor ion exchange, 300 mg of the as-synthesized MOF was mixed with 100 ml 1 M solu^on of a metalchloride salt (LiCl, NaCl or KCl) for 30 min at room temperature. A^er 30 min, the par^ally ion-exchanged MOF was separated by centrifuga^on at 2349 × g for 10 min and the process was repeatedagain for a second ^me. Therea^er, the ion-exchanged MOF was separated by centrifuga^on at 2349× for 10 min and washed three ^mes with 50 ml deionized water. A^er washing, the ion-exchangedMOF was dried in an oven at 343 K overnight. The person skilled in the art realizes that the present disclosure is not limited to the preferred embodiments described above. The person skilled in the art further realizes that modifica^ons and varia^ons are possible within the scope of the appended claims. For example, alterna^ve designs of the method depending on context may be contemplated, as well as alterna^ve MOFs, as long as the overall effects are achieved. Addi^onally, varia^ons to the disclosed embodiments can be understood and effected by the skilled person in prac^cing the claimed disclosure, from a study of the drawings, the disclosure, and the appended claims. References Long, J., Wang, S., Ding, Z., Wang, S., Zhou, Y., Huang, L., & Wang, X. (2012). Amine-func^onalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organictransforma^ons. Chemical Communica^ons, 48(95), 11656. h^ps: / / doi.org / 10.1039 / c2cc34620f DMello, M. E., Sundaram, N. G., Singh, A., Singh, A. K., & Kalidindi, S. B. (2019a). An amine func^onalized zirconium metal–organic framework as an effec^ve chemiresis^ve sensor for acidicgases. Chemical Communica^ons, 55(3), 349–352. h^ps: / / doi.org / 10.1039 / c8cc06875ePourmadadi, M., Eshaghi, M. M., Ostovar, S., Shamsabadipour, A., Safakhah, S., Mousavi, M., Rahdar, A., & Pandey, S. (2022b). UiO-66 metal-organic framework nanopar^cles as gi^ed MOFs to thebiomedical applica^on: A comprehensive review. Journal of Drug Delivery Science and Technology, 76,103758. h^ps: / / doi.org / 10.1016 / j.jddst.2022.103758Mohyuddin, A., Hussain, D., Fa^ma, B., Athar, M., Ashiq, M. N., & Najam-ul-Haq, M. (2019). Gallic acid func^onalized UiO-66 for the recovery of ribosylated metabolites from human urinesamples. Talanta, 201, 23–32. h^ps: / / doi.org / 10.1016 / j.talanta.2019.03.072E. Svensson Grape et al., J. Am. Chem. Soc.2020, 142, 39, 16795–16804 E. Svensson Grape et al., Nature Water, 2023, 433–442

Claims

Claims:

1. A method for synthesizing crystalline porous metal-organic frameworks (MOFs), comprisingmixing the following components at suitable condi^ons, including a suitable temperature anddura^on, in the presence of a suitable solvent: (a) a metal ca^on, such as zirconium;(b) a phenolic linker molecule comprising catechol and / or gallol moie^es, such as ellagateand / or ellagic acid; and (c) a ca^onic template comprising at least 5 non-hydrogen atoms;thereby obtaining the MOF material.

2. The method according to claim 1, wherein the following components are used:(a) a zirconyl chloride octahydrate compound or salt, chosen from zirconyl chlorideoctahydrate and zirconium tetrachloride; (b) ellagic acid; and / orthe ca^onic template comprising at least 5 non-hydrogen atoms is chosen from amine,ammonium, phosphonium, sulfonium, thiazolium, pyridinium, piperidinium, pyrazolium, imidazolium, alkyl, aryl and ca^onic metal complexes.

3. The method according to claim 1 or 2, wherein the MOF synthesis is performed in the presenceof water and / or ace^c acid, at a temperature of about 60-180^C, such as about 160^C, at a dura^on of about 1 hour.

4. The method according to any one of the preceding claims, wherein (a) the ca^onic template isadded in a concentra^on of at least about 0,01 ml template per ml solvent (water and / or ace^c acid), or at least about 0,03 ml template per ml solvent, or at least about 0,06 ml template per ml solvent, or at least about 0,1 ml template per ml solvent, or at least about 0,3 ml template per ml solvent, or at least about 0,6 ml template per ml solvent, or at least about 1 ml template per ml solvent and / or wherein (b) the ca^onic template is added in a concentra^on of at least about 0,1 g template per 32 mg metal ca^on, such as Zr, or at least about 0,5 g template per 32 mg metal ca^on, such as Zr, or at least about 1,0 g template per 32 mg metal ca^on, such as Zr, or at least about 5,0 g template per 32 mg metal ca^on, such as Zr and / or wherein (c)the ca^onic template is added in a molar ra^o of at least 0,5 – 2,0 mmol phenolic linker, suchas ellagic acid, per 1 mmol metal ca^on, such as Zr.

5. The method according to any one of the preceding claims, wherein the ca^onic template, in asubsequent step, is replaced, such as by ion exchange, with another ca^onic species, such as an organic ca^on, a metal ca^on or a metal complex, for subsequent use to capture a target molecule.

6. A crystalline porous metal-organic framework (MOF) material having the general formulaRz[M(HxP)YLW], wherein R is a ca^onic template comprising at least 5 non-hydrogen atoms; M= metal ca^on; P = phenolic linker molecule comprising catechol and / or gallol moie^es; L =addi^onal ligand; Z = 0.5-4; Y = 1-3; and X = 0-4; W = 0-1.

7. The crystalline porous metal-organic framework (MOF) material according to claim 6, whereinthe MOF material has pore sizes in the interval from about 5 to 15 Å, or about 0,5 to 1,5 nm.

8. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 or 7, wherein the metal ca^on is chosen from the group consis^ng of Zr(IV), Hf(V), Ti(IV) andCe(IV).

9. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 8, wherein the phenolic linker is a synthe^c or naturally occurring molecule chosen fromellagate, ellagic acid, rufigallol and other anthraquinone based catecholates and gallates, 5,5’- (1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triol) and organic linkers with two or more catecholate or gallate groups.

10. The crystalline porous metal-organic framework material (MOF) of claim 9, wherein the ellagicacid is fully protonated ellagic acid (H4EA).

11. The crystalline porous metal-organic framework material (MOF) of any one of claims 6-10,wherein the ca^onic template comprising at least 5-nonhydrogen atoms has one or more of the following features: (i) the at least 5-non-hydrogen atoms are chosen from C, N, O, S, P, halogens, metal ca^ons; (ii) the at least 5 non-hydrogen atoms comprises at least one heteroatom (not H or C), such asN, S or P, or a metal ion; (iii) the template is an organic molecule, a halocarbon or a metal complex; (iv) the template has a molecular weight (Mw) in the interval of 50 g / mol and 500 g / mol, suchas in the interval of 74 g / mol and 350 g / mol; (v) the template comprises a primary, secondary, ter^ary and / or quaternary amine;(vi) the template comprises a primary amine being a di-amine or polyamine; and(vii) the template comprises a molecular species bearing mul^ple func^onal groups having the ability to be ca^onic or become ca^onic under suitable condi^ons.

12. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 11, wherein the ca^onic template is chosen from organic ca^ons, metal ca^ons and metal-organic ca^ons, including various nitrogen based organic ca^ons, such as ammonium, pyridinium, piperidinium, pyrrolidinium, imidazolium, and pyrazolium ca^ons; phosphorus based ca^ons such as various phosphonium ca^ons; sulfur-based ca^ons including sulfonium and thiazolium compounds; metal-organic ca^ons such as metal complexes and targetmolecules to be used for adsorp^on.

13. The crystalline porous metal-organic framework (MOF) material according to claim 12,wherein the ca^onic template is chosen from the group comprising N,N-dibutylformamide(DBF), Trihexylamine (THA), Diisobutylamine (DiBA), Hexamethylenediamine (HDA), 1,4-Diazabicyclo[2.2.2]octane (DABCO), 4-tert-Butylaniline (tBAn), Tributylamine (TBA), Trioctylamine (TOA), Tetramethylammonium hydroxide (TMAOH), 2- Methylpentamethylenediamine (MPDA); Py = Pyridine, Bpy = 4,4’-Bipyridine, DMAP = 4- Dimethylaminopyridine, Ade = Adenine, DiPEA = Diisopropylethylamine, DMBPy = 5,5’- dimethyl-2,2’-bipyridine, Quin = quinine, PPA = p-phenylenediamine.

14. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 13, wherein the MOF material is chosen from the group comprising:SU-103 (HDBA)2[Zr(HxEA)2] HDBA = dibutylammoniumSU-104 (HTHA)2[Zr(HxEA)2] HTHA = trihexyammoinumSU-105 (HDiBA)2[Zr(HxEA)2] HDiBA = diisobutylammoniumSU-106 (H2DAH)[Zr(HxEA)2]H2HDA = hexamethylenediammonium SU-107 (HDABCO)2[Zr(HxEA)2] HDABCOSU-108 (HtBAn)2[Zr(HxEA)2] HtBAn = 4-tert-butylaniliniumSU-109 (HTBA)2[Zr(HxEA)2] HTBA = tributylammoniumSU-110 (HTOA)2[Zr(HxEA)2] HTOA = trioctylammoniumSU-111 (HTMA)2[Zr(HxEA)2] HTMA = TetramethylammoniumSU-112 (H2MPDA)1[Zr(HH2 xEA)2]MPDA = 2- methylpentamethylenediammonium SU-113 (HPy)2[Zr(HxEA)2.5(OAc)] HPy = pyridinium(HBPy) [ZHBPy = 4,4’-bipyridinium SU-114 2 r(HxEA)2]monoca^on (HDMAP) [Zr(H EAHDMAP = 4- SU-115 1-3 x )2(OAc)]dimethylaminopyridinium SU-116 (HAde)1-3[Zr(HxEA)2] HAde = adeninium(HDiHDiPEA = SU-117 PEA)2[Zr(HxEA)2]diisopropylethylammonium (HDABCO) [Zr(HDABCO = 1,4- SU-118 3 HxEA)3]diazabicyclo[2.2.2]octanium (HDMBPy)1-HDMBPy = 5,5’-dimethyl-2,2’- SU-119 3[Zr(HxEA)2(DMBPy)] bipyridinium SU-120 (HQuin)2[Zr(HxEA)2] HQuin = quininiumSU-121 (HPPA)2[Zr(HxEA)2.5(OAc)] HPPA = p-phenylenediaminiumSU-122 (HPPA)1-3[Zr(HxEA)2] HPPA = p-phenylenediaminium15. A crystalline porous metal-organic framework (MOF) material having the general formulaRz[M(HxP)YLW], wherein R is a ca^onic species, which species has replaced a ca^onic templateused for synthesizing the MOF material; Z = 0.5-4; Y = 1-2; M = metal ca^on, such as Zr; HxP =phenolic linker molecule comprising catechol or gallol moie^es; X = 0-4; L = addi^onal ligand;W = 0-1.

16. The crystalline porous metal-organic framework (MOF) material according to claim 15,wherein the phenolic linker molecule is ellagate and / or ellagic acid, such as fully protonatedellagic acid (H4EA).

17. The crystalline porous metal-organic framework (MOF) material according to claim 15 or 16,wherein the ca^onic species is chosen from an organic ca^on, a metal ca^on, a metal complex, or ca^onic part of a larger molecule, such as a target molecule.

18. The crystalline porous metal-organic framework (MOF) material according to any one of claims15 to 17, wherein when z = 0, the MOF material is essen^ally neutral.

19. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 18, comprising an addi^onal ligand, such as an acetate, hydroxyl, pyridyl or carboxylateligand.

20. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 19, produced by the method of any one of claims 1 to 5.

21. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 20 in the form of a powder, pellet or a powder or pellet inside a cartridge.

22. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 21, wherein the MOF material exhibits at least one property transferred from the ca^onictemplate, wherein the property is chosen from any of the following: hydrophobicity, hydrophilicity, cataly^c ac^vity,fluorescence, phosphorescence, absorbance, acidity, basicity as well as adsorbent proper^es, including the selec^ve binding of certain guest species.

23. The crystalline porous metal-organic framework (MOF) material according to any one of claims6 to 22 for use in (i) removal of pollutants and / or other chemicals, such as pharmaceu^calmolecules, in an air or waterfilter, (ii) in drug delivery, or (iii) in heterogenous catalysis.

24. Use of the crystalline porous metal-organic framework (MOF) material according to any oneof claims 6 to 23 in (a) removal of pollutants and / or other chemicals, such as pharmaceu^calmolecules, in an air or waterfilter; (b) drug delivery; or (c) heterogenous catalysis.

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