WO2021171033A1 - Procédé de synthèse d'une structure organométallique et structure organométallique - Google Patents

Procédé de synthèse d'une structure organométallique et structure organométallique Download PDF

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WO2021171033A1
WO2021171033A1 PCT/GB2021/050495 GB2021050495W WO2021171033A1 WO 2021171033 A1 WO2021171033 A1 WO 2021171033A1 GB 2021050495 W GB2021050495 W GB 2021050495W WO 2021171033 A1 WO2021171033 A1 WO 2021171033A1
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organic framework
metal organic
metal
mixed
ion
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Mario Gutiérrez Tovar
Jin-Chong Tan
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Oxford University Innovation Limited
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Priority to EP21709781.5A priority Critical patent/EP4111510A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
    • G01N33/4975—Physical analysis of biological material of gaseous biological material, e.g. breath other than oxygen, carbon dioxide or alcohol, e.g. organic vapours
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

Definitions

  • the invention provides a process for producing a metal organic framework, a metal organic framework and devices comprising a metal organic framework.
  • the invention also provides for producing a mixed-metal organic framework, a mixed metal organic framework and devices comprising the mixed-metal organic framework.
  • the invention also provides a method for detecting the presence of a volatile organic compound using the mixed-metal organic framework and a method for analysing a sample of breath from a subject.
  • Luminescent multifunctional smart-nanomaterials have aroused great interest because of their strong impact on the development of efficient and cost-effective devices in different technologies such as luminescent sensors or solid-state lighting.
  • a good luminescent nanomaterial needs to fulfil a number of requirements for being integrated into real-world devices, such as being facile and cost-effective to fabricate, have high quantum yield and be robust and reliable, among others.
  • Luminescent phototunable nanomaterials that experience changes in response to external chemical or mechanical stimuli have gained much interest, as they are ideal candidates for the fabrication of efficient non-invasive sensor devices (e.g. sensors of pollutants, volatile organic compounds, pH, pressure or thermometers) (Walekar et al., Functionalized fluorescent nanomaterials for sensing pollutants in the environment: A critical review.
  • MOFs metal-organic frameworks
  • thermochromic MOFs have been investigated because of their abilities to be exploited in the fabrication of a new generation of luminescent thermometers, which can overcome the intrinsic limitations of conventional thermometers (Cui, Y et al., Metal-organic frameworks for luminescence thermometry, Chemical communications 2015, 51 (35), 7420-7431; Rocha et al., Lanthanide Organic Framework Luminescent Thermometer, 2016, 22 (42), 14782-14795; Yue et al., Ratiometric near infrared luminescent thermometer based on lanthanide metal-organic frameworks. Journal of Solid State Chemistry 2016, 241, 99-104).
  • thermometers based on temperature-induced electrical resistance changes have inherent problems such as slow response and high sensitivity towards electric and magnetic fields (Xu et al., Highly sensitive optical thermometry through thermally enhanced near infrared emissions from Nd3+/Yb3+ codoped oxyfluoride glass ceramic, Sensors and Actuators B: Chemical 2013, 178, 520-524; Manzani et al., A portable luminescent thermometer based on green up-conversion emission of Er3+/Yb3+ co-doped tellurite glass, Scientific Reports 2017, 7, 41596).
  • liquid-based thermometers are fragile, work by contact, and are not very accurate and cannot be used in environments involving extremely high or low temperatures.
  • thermometers useless in many applications where an accurate control of the temperature is essential, such as electrical transformers in power stations, in oil refineries, coal mines or building fires
  • Xu et al. Highly sensitive optical thermometry through thermally enhanced near infrared emissions from Nd3+/Yb3+ co-doped oxyfluoride glass ceramic, Sensors and Actuators B: Chemical 2013, 178, 520-524; Manzani et al., A portable luminescent thermometer based on green up-conversion emission of Er3+/Yb3+ co-doped tellurite glass, Scientific Reports 2017, 7, 41596).
  • luminescent thermometers offer fast response, non-invasive operation and are inert to electric and magnetic fields.
  • thermometers have also attracted great attention due to their promising potential for understanding heat-transfer mechanisms occurring in living cells or integrated electronic circuits (Vetrone et al., Temperature Sensing Using Fluorescent Nanothermometers. ACS Nano 2010, 4 (6), 3254-3258; Marciniak et al., A new generation of highly sensitive luminescent thermometers operating in the optical window of biological tissues, J Mater Chem C 2016, 4 (24), 5559-5563; Brites et al., Thermometry at the nanoscale, Nanoscale 2012, 4 (16), 4799-4829).
  • thermochromic LMOFs and nanomaterials have been extensively reported, most of them are based on expensive and non-environmentally friendly rare earth metals and/or complicated synthetic methodologies (Cui et al., Metal-organic frameworks for luminescence thermometry, Chemical communications 2015, 51 (35), 7420-7431); Dingke Xue et al., High- bandwidth white-light system combining a micro-LED with perovskite quantum dots for visible light communication, ACS Appl. Mater.
  • WO2013/186542 relates to anti-bacterial applications of MOFs.
  • WO2013/186542 does not investigate or describe the luminescent properties of the materials synthesised.
  • MOFs with useful properties such as photoluminescence, electroluminescence, thermochromism and mechanochromism, which may be used in sensing devices.
  • MOFs will not use expensive and toxic elements such as rare earth metals and will be easy to synthesise via an environmentally friendly low-energy route that can readily be scaled up.
  • the present application provides an easy, cost-effective, eco-friendly, fast, and scalable route to highly photoluminescent, multistimuli-responsive (thermochromic, mechanochromic) and electroluminescent MOFs.
  • These MOFs can be synthesized following a fast and simple step reaction using an eco-friendly solvent (typically water) and mild conditions (room temperature). The synthesis is easily scaled-up, allowing the fast production of large quantities of material.
  • an eco-friendly solvent typically water
  • room temperature mild conditions
  • the synthesis is easily scaled-up, allowing the fast production of large quantities of material.
  • large amounts (10 g) of useful MOF materials for instance highly luminescent silver-containing MOFs, can be fabricated quickly (30-60 min) using mild conditions (room temperature) and an eco-friendly solvent (water).
  • This methodology has also been extrapolated to the development of other MOF materials, providing unequivocal proof that this simple and green synthetic protocol can be straightforwardly extended to numerous other Ag-MOF materials.
  • the MOFs produced via the synthetic route of the invention are very robust and exhibit exceptional photophysical properties. For example, they may be highly luminescent and exhibit high quantum yield in the solid-state ( ⁇ 60%).
  • the MOFs produced via the synthetic route of the invention also exhibit fast and reliable responses to changes in temperature and pressure, and therefore could be deployed in the fabrication of luminescent non-invasive sensors.
  • commercially available thermometers have a series of inconveniences like slow response, contact/invasive operation and high sensitivity to electromagnetic fields, which make them ineffective in demanding technological applications where an accurate temperature control is crucial at power stations, refineries, pipelines and coal mines.
  • Luminescent thermometers can overcome all these problems as they will provide a fast response, working in a non-invasive mode and are unaffected by electric fields.
  • thermometers Although some luminescent thermometers have been reported, most of them are based on expensive and non-environmentally friendly rare -earths and/or other materials obtained through a very complex, expensive and/or non-environmentally friendly synthetic protocols. Therefore, this cost-effective method allows the fabrication of a cheap materials that exhibit excellent thermochromic, mechanochromic and pH responses. Solvatochromic responses can also be achieved for sensing of chemicals such as volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • MOFs described herein behave as a good electroluminescent materials, which has permitted fabrication of a new MOF-LED (light emitting diode) using the MOF as the electroluminescent layer. This is one of very few examples of electroluminescent MOFs reported hitherto. These results illustrate the huge potential for the MOFs synthesised to be deployed in real- word technologies such as thermometers, electroluminescent devices such as LEDs, chemical sensing (for instance in medical applications), force/pressure sensing, motion sensing, vibration damage detection and also as data storage devices and optical memory devices.
  • the invention therefore provides a process for producing a metal organic framework (MOF), wherein the metal organic framework comprises one or more metal ions and one or more organic linkers, wherein the process comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a precipitate of the metal organic framework, wherein the process is performed at a temperature that does not exceed 50°C.
  • MOF metal organic framework
  • the invention also provides a metal organic framework comprising one or more metal ions and one or more organic linkers, wherein the metal organic framework is obtainable by a process which comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a precipitate of the metal organic framework, wherein the process is performed at a temperature that does not exceed 50°C.
  • the invention also provides a metal organic framework comprising a silver (Ag) ion and one or more organic linkers, wherein the metal organic framework has a photoluminescence quantum yield of greater than 50%.
  • the invention also provides a process for producing a mixed-metal organic framework (MMOF), wherein the mixed-metal organic framework comprises a first metal ion, a second metal ion and one or more organic linkers, wherein the process comprises contacting a metal organic framework comprising a first metal ion and the one or more organic linkers with a compound comprising the second metal ion in the presence of a polar protic solvent to form the mixed-metal organic framework, preferably where the polar protic solvent is water.
  • MMOF mixed-metal organic framework
  • the process comprises contacting a metal organic framework comprising a first metal ion and the one or more organic linkers with a compound comprising the second metal ion in the presence of a polar protic solvent to form the mixed-metal organic framework, preferably where the polar protic solvent is water.
  • the invention also provides a mixed-metal organic framework comprising a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • the invention also provides a method for detecting the presence of a volatile organic compound, the method comprising contacting a mixed-metal organic framework as described herein with the volatile organic compound and measuring a property of the mixed-metal organic framework.
  • the invention also provides a method for analysing a sample of breath from a subject, wherein the subject has, or is suspected of having, diabetes, said method comprising contacting the sample of breath with a mixed-metal organic framework as described herein, and measuring a property of the mixed-metal organic framework to determine the level of acetone in the sample.
  • the invention also provides a device comprising a metal organic framework or a mixed-metal organic framework as described herein, wherein the device is selected from a light emitting device, a photoluminescent device, a electroluminescent device, a luminescent thermometer, a mechanical force sensor, a chemical sensor, a motion sensing system, a data storage device, security paper, optical memory devices and vibration damage detectors.
  • the invention also provides a luminescent thermometer comprising a thermochromic metal organic framework or a mixed-metal organic framework, wherein the metal organic framework or a mixed- metal organic framework is as described herein.
  • the invention also provides a mechanical force sensor comprising a mechanochromic metal organic framework or a mixed-metal organic framework, wherein the metal organic framework or a mixed-metal organic framework is as described herein.
  • the invention also provides a chemical sensor comprising a metal organic framework or a mixed- metal organic framework as described herein.
  • the invention also provides an antibacterial material comprising a metal organic framework or a mixed-metal organic framework as described herein.
  • the invention also provides a device comprising a metal organic framework or a mixed-metal organic framework as described herein, wherein the device is an optoelectronic device, preferably wherein the device is an electroluminescent device.
  • Figure 1 shows powder X-ray diffraction (PXRD) patterns of the different OX-2 MOFs from Example 1 synthesized in methanol (OX-2 m ), methanol but using different ratio of organic linker and metal salt, 1:2 BDC:AgN03 (OX-2 m:1/2 ), DMF (OX-2 DMF ) and water (OX-2 w ).
  • the inset are photos of each powder showing the white colour of all materials with the exception of the brownish OX-2 m:1/2 .
  • Figure 2 shows field emission scanning electron microscopy (FESEM) micrographs of (A-B) OX- 2 W and (C-D) OX-2 m:1/2 .
  • Figures 2 (E-J) show energy-dispersive X-ray (EDX) FESEM (FESEM- EDX) images of the different crystals found in OX-2 m:1/2 MOF, showing the distribution of Ag ( Figures 2F and 21) and C ( Figures 2G and 2J) in the selected crystals.
  • FESEM- EDX energy-dispersive X-ray
  • Figure 3A shows the excitation-emission map representation of OX-2 m
  • Figure 3B shows the excitation-emission map representation of OX-2 m:1/2
  • Figure 3C 3B shows the excitation-emission map representation of OX-2 DMF
  • Figure 3D 3B shows the excitation-emission map representation of OX-2 w recorded in the solid-state.
  • the quantum yield recorded using an excitation wavelength of 330-nm, along with a photo of each sample under UV-irradiation (365- nm) are depicted as inset.
  • Figure 4A and 4B show PXRD patterns and emission spectra of OX-2 pellets compressed at different pressures (indicated as inset).
  • Figures 4C and 4D show PXRD patterns and emission spectra of OX-2 powders obtaining by grinding the former pellets.
  • Figure 5A shows the emission spectra of OX-2 collected by exposing it to increasing temperatures.
  • the inset is a representation of the I 0 -I vs T showing a linear response offered by OX-2 to changes in the temperature.
  • Figure 5B shows the emission spectra of OX-2 recorded at 25 and 100°C by heating-up and cooling down successively the material.
  • the inset is a representation of the excellent repeatability and reproducibility exhibited by OX-2 to changes in the temperature.
  • Figures 6A and 6B show photographs of the OX-2 pellet (A) and film (B) upon cyclically exposing to high (200-220°C) and room (25°C) temperature conditions.
  • Figure 7 shows the Fourier transform infrared (FTIR) spectra of OX-2m, OX-2m:1/2, OX-2DMF and OX-2w.
  • Figure 8A shows the FESEM micrograph of OX-2 m MOF.
  • Figure 8B shows the FESEM micrograph of OX-2 DMF MOF.
  • Figures 9A and 9B show AFM topography images of the elongated nanoplates of OX-2 w .
  • Figures 9C and 9D show thickness profiles of the OX-2 w elongated nanoplates obtained from the AFM image in 9A and 9B respectively, showing a thickness of tens of nm.
  • Figures 10 A to C show FESEM-EDX micrographs of OX-2 m:1/2 .
  • Figures 10 D to F show FESEM- EDX micrographs of OX-2 w , showing the “flower” shaped crystals and the homogeneously distributed elongated nanoplates, respectively.
  • Figure 11 shows nanosecond-picosecond emission decays of 11A) BDC linker, 12B) OX-2 DMF ,
  • Figure 12 shows a comparison of the PXRD pattern of the [Ag-(BDC) 1/2 ] n reported and those of OX-2 w MOFs obtained through a small scale synthesis (hundreds of mg) and a scaled-up synthesis (10 mg).
  • Figure 13 shows the excitation-emission map of the OX-2 w obtained through the scaled-up method.
  • Figure 14 shows PXRD patterns of OX-2 w after being soaked in water for several periods (up to 21 days).
  • Figure 15 shows PXRD patterns of OX-2 w MOF as synthetized and after being exposed to ambient conditions in the lab (day light, ⁇ 40% humidity, solvent vapours, etc) for 70 days.
  • Figure 16 shows emission of spectra of OX-2w MOF before and after being exposed to ambient conditions in the laboratory (day light, ⁇ 40% humidity, solvent vapours, etc) for different periods (up to 70 days). The inset shows a minimal decrease in the quantum yield values from 60% to 57%.
  • Figures 17A and 17B show PXRD patterns and emission spectra of OX-2 pellets compressed at different pressures for second time.
  • Figures 18C and 18D show PXRD patterns and emission spectra of OX-2 powders obtaining by grinding the former pellets.
  • metal organic framework or “MOF” is known in the art, and takes its normal meaning herein. Thus, the term refers to a compound comprising metal ions coordinated to organic ligands to form an extended one-, two-, or three-dimensional structure. Often, the structure is an extended two- or three-dimensional structure. It may for instance be an extended three-dimensional structure.
  • a “mixed-metal organic framework” refers to a MOFs comprising at least two types of metal ion.
  • crystalline indicates a crystalline compound, which is a compound having along-range ordered structure.
  • a crystalline compound is typically in the form of crystals or, in the case of a polycrystalline compound, crystallites (i.e. a plurality of crystals having particle sizes of less than or equal to 1 ⁇ m). The crystals together often form a layer.
  • the crystals of a crystalline material may be of any size.
  • room temperature refers to the conventional definition of room temperature of between 15 and 25°C.
  • organic linker indicates an organic molecule comprising two or more coordination sites suitable for coordinating to metal ions.
  • an organic linker typically comprises two or more functional groups capable of coordinating to metal ions.
  • nanoparticle means a microscopic particle whose size is typically measured in nanometres (nm).
  • a nanoparticle typically has a particle size of from 0.1 nm to 1000 from 0.1 nm to 1000 nm, for instance from 1 nm to 750 nm, from 10 nm to 500 nm.
  • a nanoparticle is a particle having a size of from 50 to 500 nm, from 100 nm to 500 nm, or from 250 nm to 500 nm.
  • halide indicates the singly charged anion of an element in group VIIA of the periodic table.
  • Halide includes fluoride, chloride, bromide and iodide.
  • alkyl refers to a linear or branched chain saturated hydrocarbon radical.
  • An alkyl group may be a C 1-20 alkyl group, a C 1-14 alkyl group, a C 1- 10 alkyl group, a C 1-6 alkyl group or a C 1-4 alkyl group.
  • Examples of a C 1- 10 alkyl group are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
  • Examples of C 1-6 alkyl groups are methyl, ethyl, propyl, butyl, pentyl or hexyl.
  • C 1-4 alkyl groups are methyl, ethyl, i-propyl, n-propyl, t-butyl, s-butyl or n-butyl. If the term “alkyl” is used without a prefix specifying the number of carbons, it typically has from 1 to 6 carbons (and this also applies to any other organic group referred to herein).
  • aryl refers to a monocyclic, bicyclic or polycyclic aromatic ring which contains from 6 to 14 carbon atoms, typically from 6 to 10 carbon atoms, in the ring portion. Examples include phenyl, naphthyl, indenyl, indanyl, anthrecenyl and pyrenyl groups.
  • aryl group includes heteroaryl groups.
  • heteroaryl refers to monocyclic or bicyclic heteroaromatic rings which typically contain from six to ten atoms in the ring portion including one or more heteroatoms.
  • a heteroaryl group is generally a 5- or 6- membered ring, containing at least one heteroatom selected from O, S, N, P, Se and Si. It may contain, for example, one, two or three heteroatoms.
  • heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, pyrazolidinyl, pyrrolyl, oxazolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolyl and isoquinolyl.
  • alkylene group refers to a substituted or unsubstituted bidentate moiety obtained by removing two hydrogen atoms, either both from the same carbon atom, or one from each of two different carbon atoms, of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise specified), which may be aliphatic or alicyclic, and which may be saturated, partially unsaturated, or fully unsaturated.
  • alkylene includes the sub-classes alkenylene, alkynylene, cycloalkylene, etc., discussed below. Typically it is C 1- 10 alkylene, for instance C 1-6 alkylene.
  • C 1-4 alkylene for example methylene, ethylene, i-propylene, n-propylene, t-butylene, s-butylene or n-butylene. It may also be pentylene, hexylene, heptylene, octylene and the various branched chain isomers thereof.
  • An alkylene group may be substituted or unsubstituted, for instance, as specified above for alkyl. Typically a substituted alkylene group carries 1, 2 or 3 substituents, for instance 1 or 2.
  • the prefixes denote the number of carbon atoms, or range of number of carbon atoms.
  • C 1-4 alkylene as used herein, pertains to an alkylene group having from 1 to 4 carbon atoms.
  • groups of alkylene groups include C 1-4 alkylene ("lower alkylene”), C 1-7 alkylene, C 1-10 alkylene and C 1-20 alkylene.
  • linear saturated C 1-7 alkylene groups include, but are not limited to, -(CH 2 ) n - where n is an integer from 1 to 7, for example, -CH 2 - (methylene), -CH 2 CH 2 - (ethylene), -CH 2 CH 2 CH 2 - (propylene), and -CH 2 CH 2 CH 2 CH 2 - (butylene).
  • branched saturated C 1-7 alkylene groups include, but are not limited to, -CH(CH 3 )-, -CH(CH 3 )CH 2 -, -CH(CH 3 )CH 2 CH 2 -, -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, -
  • Partially unsaturated alkylene groups comprising one or more double bonds may be referred to as alkenylene groups.
  • Partially unsaturated alkylene groups comprising one or more triple bonds may be referred to as alkynylene groups (for instance -C ⁇ C-, CH 2 -C ⁇ C-, and -CH 2 -C ⁇ C-CH 2 -).
  • alicyclic saturated C 1-7 alkylene groups include, but are not limited to, cyclopentylene (e.g., cyclopent- 1 ,3 -ylene), and cyclohexylene (e.g., cyclohex-1, 4-ylene).
  • Examples of alicyclic partially unsaturated C 1-7 alkylene groups include, but are not limited to, cyclopentenylene (e.g., 4-cyclopenten-1,3-ylene), cyclohexenylene (e.g., 2-cyclohexen-1, 4-ylene; 3-cyclohexen-1,2-ylene; 2, 5-cyclohexadien-1, 4-ylene). Such groups may also be referred to as “cycloalkylene groups”.
  • arylene group refers to a substituted or unsubstituted bidentate moiety obtained by removing two hydrogen atoms, either both from the same carbon atom, or one from each of two different carbon atoms, of an aryl group, as defined herein.
  • arylene includes phenylene, naphthylene, indenylene, indanylene, anthrecenylene and pyrenylene groups, and also heteroarylene groups such as pyridylene, pyrazinylene, pyrimidinylene, pyridazinylene, furanylene, thienylene, pyrazolidinylene, pyrrolylene, oxazolylene, oxadiazolylene, isoxazolylene, thiadiazolylene, thiazolylene, isothiazolylene, imidazolylene, pyrazolylene, quinolylene and isoquinolylene.
  • substituted refers to an organic group which bears one or more substituents selected from C 1- 10 alkyl, aryl (as defined herein), cyano, amino, nitro, C 1- 10 alkylamino, di(C 1-10 )alkylamino, arylamino, diarylamino, aryl( C 1- 10 )alkylamino, amido, acylamido, hydroxy, oxo, halo, carboxy, ester, acyl, acyloxy, C 1- 10 alkoxy, aryloxy, halo( C 1- 10 ) alkyl, sulfonic acid, thiol, C 1- 10 alkylthio, arylthio, sulfonyl, phosphoric acid, phosphate ester, phosphonic acid and phosphonate ester.
  • substituents selected from C 1- 10 alkyl, aryl (as defined herein), cyano, amino, nitro, C 1- 10 alkylamino,
  • substituted alkyl groups include haloalkyl, perhaloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl and alkaryl groups.
  • a group When a group is substituted, it may bear 1, 2 or 3 substituents.
  • a substituted group may have 1 or 2 substituents.
  • optical device refers to devices which source, control, detect or emit light. Light is understood to include any electromagnetic radiation. Examples of optoelectronic devices include photovoltaic devices, photodiodes (including solar cells), phototransistors, photomultipliers, photoresistors, light emitting devices, electroluminescent devices, light emitting diodes and charge injection lasers. Often, an “optoelectronic device” that is referred to herein is an electroluminescent device.
  • electrostatic device refers to a light-emitting device comprising a material that accepts charge, both electrons and holes, which subsequently recombine and emit light.
  • n-type layer refers to a layer of an electron-transporting (i.e. an n-type) material.
  • An electron-transporting (i.e. an n-type) material could, for instance, be a single electron-transporting compound or elemental material.
  • An electron-transporting compound or elemental material may be undoped or doped with one or more dopant elements.
  • p-type layer refers to a layer of a hole-transporting (i.e. a p-type) material.
  • a hole- transporting (i.e. a p-type) material could be a single hole-transporting compound or elemental material, or a mixture of two or more hole-transporting compounds or elemental materials.
  • a hole- transporting compound or elemental material may be undoped or doped with one or more dopant elements.
  • electrostatic material refers to a material that accepts charge, both electrons and holes, which subsequently recombine and emit light.
  • photoluminescent material refers to a material that is able to absorb photons and undergo photoexcitation, then emit photons.
  • imidazole-based linker refers to any organic linker comprising a substituted or unsubstituted imidazole group, or an ionic version thereof, for instance a substituted or unsubstituted imidazolate anion.
  • aromatic carboxylate ion linker refers to any organic linker comprising a carboxylate group and an aromatic group.
  • the present invention provides a process for producing a metal organic framework (MOF), wherein the metal organic framework comprises one or more metal ions and one or more organic linkers, wherein the process comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a precipitate of the metal organic framework, wherein the process is performed at a temperature that does not exceed 50°C.
  • MOF metal organic framework
  • the MOF is crystalline.
  • the process comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a crystalline precipitate.
  • the precipitate of the metal organic framework forms within 10 minutes of contacting the one or metal ions with the one or more linkers, for instance within 5 minutes, within 2 minutes, within 1 minute or within 30 seconds of contacting the one or metal ions with the one or more linkers.
  • the formation of the metal organic framework by the process described herein is distinguished from processes in which large crystals (hundreds of microns in size) are slowly grown from solution over a period of hours or even days.
  • the metal organic framework is precipitated as a bulk solid.
  • a bulk solid is an assembly of solid particles that is large enough for the statistical mean of any property to be independent of the number of particles.
  • the metal organic framework typically comprises a large number of small crystals.
  • the crystals of the metal organic framework in the precipitate have an average maximum dimension of less than 500 ⁇ m, for instance of less than 100 ⁇ m, of less than 50 ⁇ m, preferably less than 10 ⁇ m.
  • the crystals of the metal organic framework in the precipitate have an average maximum dimension of less than 5 ⁇ m, more preferably less than 2 ⁇ m.
  • the nanoparticles are plate-shaped.
  • the metal organic framework precipitates as nanoparticles.
  • the metal organic framework typically consists of particles having an average maximum dimension of from 0.1 nm to 1000 nm, for instance from 1 nm to 750 nm, from 10 nm to 500 nm, or for example from 50 to 500 nm, from 100 nm to 500 nm, or from 250 nm to 500 nm.
  • the metal organic framework consists of particles having an average maximum dimension of from 250 to 450 nm, for instance from 300 to 400 nm.
  • the nanoparticles are in the form of nanoplates.
  • the process is performed at a temperature that does not exceed 50°C.
  • the process is performed at a temperature that does not exceed 40°C, for instance at a temperature that does not exceed 30°C.
  • the process is performed at a temperature of from 0 to 30°C, typically from 10 to 30°C, for instance from 20 to 30°C.
  • the process is typically performed at room temperature, for instance at a temperature of from 15 to 25°C, typically about 20°C.
  • the process refers to the process for producing the metal organic framework, rather than any subsequent processing that may be performed on the metal organic framework e.g. drying.
  • one or more metal ions is meant one or more kinds of metal ions, i.e. the MOF may comprise only one kind of metal ion or may comprise two or more kinds of metal ions. The kinds of metal ions may differ by charge and/or element. Typically, the MOF comprises one kind of metal ion or two kinds of metal ions.
  • the one or more metal ions comprise one or more metal ions of group 9, 10, 11, 12 or 14 of the periodic table.
  • the one or more metal ions may consist of ions of metals selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg) and lead (Pb).
  • the one or more metal ions may be transition metal ions.
  • the one or more metal ions comprise one or more ions selected from Ag, Au, Cu, Cd, Ir, Pt, Pd and Pb ions.
  • the one or more metal ions comprise Ag ions, typically Ag + ions.
  • the one or more metal ions may consist of Ag ions, typically an Ag + ions.
  • the process comprises a step of dissolving a salt of the one or more metal ions in an aqueous solution.
  • the salt comprises one or more metal ions, as described herein, and a counterion.
  • the counterion is selected from the group consisting of halide ions, nitrate ions, sulfate ions, hydroxide ions, or organic anions such as carboxylate anions.
  • the counterion may be selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate (acetate).
  • the salt may be selected from a salt comprising a metal selected from groups 9, 10, 11,12 or 14 of the periodic table, and a counterion selected from the group consisting of halide ions, nitrate ions, sulfate ions, hydroxide ions, or organic anions such as carboxylate anions, preferably from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate.
  • the salt may be a salt comprising an Ag, Au, Cu, Cd, Ir, Pt, Pd or Pb ion, preferably an Ag ion, and a counterion selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate.
  • the salt may be silver nitrate (AgNO 3 ), silver chloride (AgCl) or silver acetate (CH 3 CO 2 Ag).
  • the aqueous solution is typically water.
  • the process comprises a step of dissolving a salt of the one or more metal ions, as defined herein, in water.
  • one or more organic linkers is meant one or more kinds of organic linkers i.e. the metal organic framework may comprise only one kind of organic linker or may comprise two or more kinds or organic linker. Typically, the metal organic framework comprises one kind of organic linker or two kinds of organic linker.
  • the one or more organic linkers are selected from carboxylate ion linkers and imidazole- based linkers.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers and imidazole-based linkers.
  • the metal organic framework may comprise one kind of organic linker or two kinds of organic linker.
  • the metal organic framework may comprise one kind of organic linker that is a carboxylate ion linker.
  • the metal organic framework may comprise one kind of organic linker that is an imidazole-based linker.
  • the metal organic framework may comprise both carboxylate ion linkers and an imidazole-based linkers.
  • the process typically comprises a step of deprotonating an aromatic carboxylic acid with a base to produce the aromatic carboxylate ion linker.
  • the base may be any base known to the skilled person suitable for deprotonating an aromatic carboxylic acid to produce the carboxylate anion.
  • the base may be an amine or a metal hydroxide.
  • the base is trimethylamine (NEt 3 ) or sodium hydroxide (NaOH).
  • the process may comprise a step of deprotonating an aromatic carboxylic acid by dissolving the aromatic carboxylic acid in a solvent, preferably in water, to form the aromatic carboxylate ion linker.
  • the process may comprise dissolving a salt of an aromatic carboxylic acid in a solvent, preferably water, to form the aromatic carboxylate ion linker.
  • the aromatic carboxylic acid or the salt of an aromatic carboxylic acid dissociates to form the aromatic carboxylate ion linker in solution in the solvent.
  • the process may comprise a step of deprotonating an imidazole derivative with a base to produce the imidazole- based linker.
  • the process may comprise a step of deprotonating an organic linker comprising a substituted or unsubstituted imidazole group to produce an organic linker comprising a substituted or unsubstituted imidazolate group.
  • the base is an amine or a metal hydroxide.
  • the base is trimethylamine (NEt 3 ) or sodium hydroxide (NaOH).
  • the aromatic carboxylate ion linker comprises two or more carboxylate groups.
  • the aromatic carboxylate ion linker may comprise three or more carboxylate groups.
  • the aromatic carboxylate ion linker comprises two or three carboxylate groups.
  • the aromatic carboxylate ion linker typically comprises a substituted or unsubstituted aryl group, typically a substituted or unsubstituted aryl group selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted indenyl, substituted or unsubstituted indanyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted pyrenyl and substituted or unsubstituted 1 , 3, 5-triphenyl benzene.
  • a substituted or unsubstituted aryl group selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted indenyl
  • the substituted or unsubstituted aryl group is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted biphenyl and substituted or unsubstituted 1, 3, 5-triphenyl benzene.
  • the aromatic carboxylate ion linker comprises a phenyl group, a napthyl group, a biphenyl group or 1, 3, 5-triphenyl benzene substituted with two or more carboxylate groups.
  • the aromatic carboxylate ion linker may comprise a phenyl group, a napthyl group, a biphenyl group or 1, 3, 5-triphenyl benzene substituted with three or more carboxylate groups.
  • the aromatic carboxylate ion linker comprises a phenyl group, a napthyl group, a biphenyl group or 1, 3, 5-triphenyl benzene substituted with two or three carboxylate groups.
  • the aromatic carboxylate ion linker is typically selected from an ion of a substituted or unsubstituted benzene dicarboxylic acid, an ion of a substituted or unsubstituted benzene tricarboxylic acid, an ion of a substituted or unsubstituted naphthalene dicarboxylic acid, an ion of a substituted or unsubstituted biphenyl dicarboxylic acid, or an ion of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • the aromatic carboxylate ion linker is selected from an ion of a compound from the group consisting of
  • R and R’ are selected from H, OH, NH 2 , CH 3 , CN, NO 2 , F, Cl, Br, I, -OC 3 H 5 , OC 7 H 7 .
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate), benzene-1, 3-dicarboxylate (isophthalate), benzene-1, 2-dicarboxylate (phthalate), naphthalene-2, 6- dicarboxylate or naphthalene-1, 4-dicarboxylate.
  • the aromatic carboxylate ion linker is benzene-1 , 4-dicarboxylate (terephthalate).
  • the imidazole-based linker is an imidazolate linker of formula (I) or an imidazole linker of formula (II):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, C 1- 10 alkyl, C 2- 10 alkenyl, C 2- 10 alkynyl, cyano, and halogen, provided that R 2 and R 3 or R 6 and R 7 may be joined so as to form a substituted or unsubstituted ring, preferably wherein R 2 and R 3 or R 6 and R 7 are joined to form a 5 or 6-membered ring, optionally wherein the ring comprises 1, 2 or 3 heteroatoms selected from O, N and S, and provided that any one of R 1 to R 7 may be a hydrocarbon linker bonded to a further substituted or unsubstituted imidazole or imidazolate ring.
  • the hydrocarbon linker may be selected from the group consisting of alkylene, arylene, alkylene- arylene, alkylene-arylene-alkylene-, for instance from the group consisting of C 1-10 alkylene, C 6-10 arylene, C 1-10 alkylene -C 6-10 arylene, C 1-10 alkylene -C 6-10 arylene - C 1-10 alkylene-.
  • the imidazole-based linker may comprise two substituted or unsubstituted imidazole or imidazolate rings joined by a hydrocarbon linker.
  • the imidazole-based linker is an imidazolate linker of formula (I) or an imidazole linker of formula (II), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, cyano, and halogen, provided that R 2 and R 3 or R 6 and R 7 may be joined so as to form a substituted or unsubstituted 5 or 6-membered ring, optionally wherein the ring comprises 1, 2 or 3 heteroatoms selected from O, N and S.
  • the imidazole-based linker is selected from the group consisting of wherein R 6 , and R 7 are selected from H, methyl, CN and Cl.
  • the imidazole-based linker may be selected from the group consisting of imidazole, 2-methylimidazole and 4,5- dichloroimidazole.
  • the one or more metal ions comprise an Ag ion
  • the one or more organic linkers comprise a terephthalate linker.
  • the one or more metal ions are Ag ions and the one or more organic linkers are terephthalate linkers.
  • the metal organic framework further comprises water of crystallization.
  • the metal organic framework may comprise water molecules coordinated to the one or more metal ions and/or the one or more organic linkers.
  • the metal organic framework may comprise Ag ions and the water molecules may be coordinated to the Ag ions.
  • the only solvent molecules present in the metal organic framework are water molecules.
  • the process comprises contacting an aqueous solution of the one or more metal ions with an aqueous solution of the one or more organic linkers.
  • the process may comprise mixing an aqueous solution of the one or more metal ions with an aqueous solution of the one or more organic linkers.
  • the aqueous solution of the one or more metal ions is a solution of the one or more metal ions in a solvent comprising at least 50% water, at least 75% water, at least 90% water, for instance at least 95% water or at least 99% water.
  • the aqueous solution of the one or more metal ions is a solution of the one or more metal ions in water.
  • the aqueous solution of the one or more organic linkers is a solution of the one or more organic linkers in a solvent comprising at least 50% water, at least 75% water, at least 90% water, for instance at least 95% water or at least 99% water.
  • the aqueous solution of the one or more organic linkers is a solution of the one or more organic linkers in water.
  • the only solvent present may be water.
  • the only solvent used in the process is water.
  • the molar ratio of metal ion to linker used in the process is typically between 1 : 1 and 1:10.
  • the molar ratio of metal ion to linker may be between 1 : 1 and 1 : 5, for instance between 1 : 1 and 1 :3.
  • the molar ratio of metal ion to linker may be about 1:5, 1 :4, 1 :3 or 1 :2.
  • the molar ratio of metal ion to linker is 1 :2.
  • the process may further comprise recovering the metal organic framework.
  • the skilled person would be well of methods for recovering the precipitate of the metal organic framework.
  • the process may comprise isolating the precipitate of the metal organic framework by filtration, by centrifugation or by removing the surrounding solvent.
  • the step of recovering the metal organic framework may comprise one or more optional washing steps, where the metal organic framework is washed with a solvent, preferably where the metal organic framework is washed with water.
  • the step of recovering the metal organic framework may comprise one or more drying steps where the solvent is removed.
  • the invention also provides a metal organic framework comprising one or more metal ions, as defined herein, and one or more organic linkers, as defined herein, wherein the metal organic framework is obtainable by a process which comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a precipitate of the metal organic framework, wherein the process is performed at a temperature that does not exceed 50°C.
  • the process may contain any of the process features described herein.
  • the invention also provides a metal organic framework comprising a silver ion and one or more organic linkers, wherein the metal organic framework has a photoluminescence quantum yield of greater than 50%.
  • the metal organic framework may have a photoluminescence quantum yield of at least 55%, preferably at least 60%. Typically, the photoluminescence quantum yield is measured at an excitation wavelength of 330nm.
  • the metal organic framework is crystalline.
  • the metal organic framework is in the form of a bulk solid.
  • a bulk solid is an assembly of solid particles that is large enough for the statistical mean of any property to be independent of the number of particles.
  • the metal organic framework typically comprises a large number of small crystals.
  • the crystals of the metal organic framework in the precipitate have an average maximum dimension of less than 500 ⁇ m, for instance of less than 100 ⁇ m, of less than 50 ⁇ m, preferably less than 10 ⁇ m.
  • the crystals of the metal organic framework have an average maximum dimension of less than 5 ⁇ m, more preferably less than 2 ⁇ m.
  • the metal organic framework is in the form of nanoparticles.
  • the metal organic framework typically consists of particles having an average maximum dimension of from 0.1 nm to 1000 nm, for instance from 1 nm to 750 nm, from 10 nm to 500 nm, or for example from 50 to 500 nm, from 100 nm to 500 nm, or from 250 nm to 500 nm.
  • the metal organic framework consists of particles having an average maximum dimension of from 250 to 450 nm, for instance from 300 to 400 nm
  • the nanoparticles are plate -shaped.
  • the one or more organic linkers are as defined herein.
  • the one or more organic linkers comprise an ion of a substituted or unsubstituted benzene dicarboxylic acid, an ion of a substituted or unsubstituted benzene tricarboxylic acid, an ion of a substituted or unsubstituted naphthalene dicarboxylic acid, an ion of a substituted or unsubstituted biphenyl dicarboxylic acid, or an ion of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • the one or more organic linkers comprise a terephthalate linker.
  • the metal organic framework may comprise a silver ion and a terephthalate linker.
  • the metal organic framework comprises water of crystallisation.
  • the metal organic framework may comprise water molecules coordinated to the one or more metal ions and/or the one or more organic linkers.
  • the metal organic framework may also comprise water molecules coordinated to the Ag ions.
  • the invention also provides a metal organic framework comprising one or more metal ions, as defined herein, and one or more organic linkers, as defined herein and water of crystallisation.
  • a metal organic framework comprising one or more metal ions, as defined herein, and one or more organic linkers, as defined herein and water of crystallisation.
  • the only solvent molecules present in the metal organic framework are water molecules.
  • the invention also provides a process for producing a mixed-metal organic framework (MMOF), wherein the mixed-metal organic framework comprises a first metal ion, a second metal ion and one or more organic linkers, wherein the process comprises contacting a metal organic framework comprising a first metal ion and the one or more organic linkers with a compound comprising the second metal ion in the presence of a polar protic solvent to form the mixed-metal organic framework.
  • MMOF mixed-metal organic framework
  • the polar protic solvent is a solvent selected from the group consisting of a C1 -10 alcohol, water or mixtures thereof.
  • the polar protic solvent may be a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, water and mixtures thereof.
  • the polar protic solvent is water.
  • the process usually comprises contacting the metal organic framework with a compound comprising the second metal ion and the polar protic solvent.
  • the process comprises contacting the metal organic framework with a compound comprising the second metal ion and water.
  • the process comprises mixing the metal organic framework with a compound comprising the second metal ion to create a mixture, then contacting the mixture with the polar protic solvent to form the mixed-metal organic framework.
  • the process may comprise mixing the metal organic framework with a compound comprising the second metal ion to create a mixture, then contacting the mixture with water to form the mixed-metal organic framework.
  • the metal organic framework and the compound comprising the second metal ion are both solids.
  • the process may comprise grinding the metal organic framework and the compound comprising the second metal ion together to form a mixture, then contacting the mixture with a polar protic solvent, preferably water, to form the mixed-metal organic framework.
  • the metal organic framework and the compound comprising the second metal ion may both be powders.
  • the process may comprise mixing a powder of the metal organic framework with a powder of a compound comprising the second metal ion to create a mixture, then contacting the mixture with a polar protic solvent, preferably water, to form the mixed-metal organic framework.
  • the polar protic solvent may be present in liquid form, or may be present in the surrounding atmosphere as a vapour.
  • the humidity of the air may be sufficient to facilitate conversion of the metal organic framework to a mixed-metal organic framework.
  • the process may comprise contacting the metal organic framework with a compound comprising the second metal ion and a vapour of the polar protic solvent, preferably water vapour.
  • the polar protic solvent may be added to the metal organic framework and the compound comprising the second metal ion as a liquid.
  • the process may comprise contacting the metal organic framework with a compound comprising the second metal ion and the polar protic solvent in liquid form, preferably liquid water.
  • the metal organic framework comprising a first metal ion and the one or more organic linkers may be any metal organic framework as defined herein.
  • the first and second metal ions are metal ions of group 9, 10, 11, 12 or 14 of the periodic table.
  • the first and second metal ions may be selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg) and lead (Pb).
  • the first and second metal ions may be transition metal ions.
  • the first and second metal ions are selected from the group consisting of Zn, Ag, Au, Cu, Cd, Ir, Pt, Pd and Pb ions.
  • the first metal ion is a Zn ion, for instance a Zn 2+ ion
  • the second metal ion is an Ag ion, for instance a Ag + ion.
  • the compound comprising the second metal ion is a salt of the second metal ion.
  • the salt comprises the second metal ion, as described herein, and a counterion.
  • the counterion is selected from the group consisting of halide ions, nitrate ions, sulfate ions, hydroxide ions, or organic anions such as carboxylate anions.
  • the counterion may be selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate (acetate).
  • the salt may be selected from a salt of a metal selected from groups 9, 10, 11, 12 or 14 of the periodic table, with a counterion selected from the group consisting of halide ions, nitrate ions, sulfate ions, hydroxide ions, or organic anions such as carboxylate anions, preferably from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate.
  • the salt may be a salt of an Zn, Ag, Au, Cu, Cd, Ir, Pt, Pd or Pb ion, preferably Ag, with a counterion selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate or ethanoate.
  • the salt may be silver nitrate (AgNO 3 ), silver chloride (AgCl) or silver actetate (CH 3 CO 2 Ag).
  • the salt of the second metal ion is a salt of formula MX n , wherein M represents the second metal ion; Xis an anion selected from halide, nitrate or CH 3 COO; and where depends on the charge of the second metal ion, M, and the charge of the anion, X.
  • the salt of the second metal ion is a salt of formula MX wherein M represents the second metal ion; Xis an anion selected from halide, nitrate or CH 3 COO-.
  • the one or more organic linkers may be any organic linkers as defined herein. Typically, the one or more organic linkers are selected from aromatic carboxylate ion linkers and imidazole-based linkers.
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (isophthalate).
  • the aromatic carboxylate ion linker is benzene-1 , 4-dicarboxylate (terephthalate).
  • the invention also provides a mixed-metal organic framework obtainable by the process for producing a mixed-metal organic framework as defined herein.
  • the invention also provides a mixed-metal organic framework comprising a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • the one or more organic linkers may be any organic linkers as defined herein.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers and imidazole-based linkers.
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (isophthalate).
  • the aromatic carboxylate ion linker is benzene-1 , 4-dicarboxylate (terephthalate).
  • the invention provides a device comprising a mixed-metal organic framework as defined herein, wherein the device is a chemical sensor.
  • a chemical sensor is a device for detecting the presence of a particular chemical or group of chemicals.
  • the mixed-metal organic framework in the chemical sensor undergoes a change when exposed to a chemical of interest.
  • the mixed-metal organic framework may be photoluminescent, and the photoluminescence properties of the mixed-metal organic framework change in the presence of the chemical of interest.
  • the emission intensity may increase or decrease, and/or the colour of the emitted light may change upon exposure of the mixed-metal organic framework to the chemical of interest.
  • the device is a chemical sensor for detecting a volatile organic compound (VOC).
  • VOC volatile organic compound
  • the device is a chemical sensor for detecting acetone.
  • the device comprises a mixed-metal organic framework comprising a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from an ion of a substituted or unsubstituted benzene dicarboxylic acid, an ion of a substituted or unsubstituted benzene tricarboxylic acid, an ion of a substituted or unsubstituted naphthalene dicarboxylic acid, an ion of a substituted or unsubstituted biphenyl dicarboxylic acid, or an ion of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • aromatic carboxylate ion linkers preferably from an ion of a substituted or unsubstituted benzene dicarboxylic acid, an ion of a substituted or unsubstituted benzene tricarboxylic acid, an ion of a substituted or unsubstitute
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (phthalate).
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate).
  • the chemical sensor typically comprises a mixed-metal organic framework comprising zinc ions, a silver ions and terephthalate ions.
  • the invention therefore also provides a method for detecting the presence of a volatile organic compound, the method comprising contacting a mixed-metal organic framework as defined herein with the volatile organic compound and measuring a property of the mixed-metal organic framework.
  • Contacting the mixed-metal organic framework with the volatile organic compound may comprise contacting the mixed-metal organic framework with a liquid comprising the volatile organic compound, or contacting the mixed-metal organic framework with a vapour of the volatile organic compound.
  • the mixed-metal organic framework is photoluminescent, and the property of the mixed- metal organic framework is photoluminescence, for instance fluorescence.
  • the photoluminescence properties of the mixed-metal organic framework may change in the presence of the chemical of interest, for example, the emission intensity may increase or decrease, and/or the colour of the emitted light may change upon exposure of the mixed-metal organic framework to the volatile organic compound of interest.
  • the emission is decreased (quenched) in the presence of the volatile organic compound of interest.
  • the property may be fluorescence and measuring a property of the mixed-metal organic framework comprises measuring the emission spectrum of the metal organic framework.
  • the volatile organic compound is acetone.
  • the mixed-metal organic framework may be any mixed-metal organic framework as described herein.
  • the mixed-metal organic framework comprises a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions of a substituted or unsubstituted biphenyl dicarboxylic acid, or ions of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • aromatic carboxylate ion linkers preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (phthalate).
  • the aromatic carboxylate ion linker is benzene - 1 , 4-dicarboxylate (terephthalate).
  • the method is a method for detecting acetone may comprising contacting a mixed-metal organic framework comprising zinc ions, silver ions and terephthalate ions with acetone and measuring a property of the mixed-metal organic framework.
  • the property is fluorescence and measuring a property of the mixed-metal organic framework comprises measuring the emission spectrum of the metal organic framework.
  • the emission of the mixed-metal organic framework is decreased (i.e. is quenched) in the presence of acetone.
  • the invention also provides a method for analysing a sample of breath from a subject, wherein the subject has, or is suspected of having, diabetes, said method comprising contacting the sample of breath with a mixed-metal organic framework as described herein, and measuring a property of the mixed-metal organic framework to determine the level of acetone in the sample.
  • acetone in the breath is an indicator of elevated levels of ketones in the blood (diabetic ketoacidosis), which indicate a lack of insulin.
  • a lack of insulin in the bloodstream allows unregulated fatty acid release from adipose tissue which increases fatty acid oxidation to acetyl CoA, some of which is diverted to ketogenesis. This raises ketone levels significantly above what is seen in normal physiology. Serious side effects can result if insulin is not administered. It is therefore useful to have a quick and reliable method for detecting acetone on the breath to determine whether a subject who has, or is suspected of having, diabetes, might require medical attention.
  • the mixed-metal organic framework is photoluminescent, and the property of the mixed- metal organic framework measured may be photoluminescence, for instance fluorescence.
  • the photoluminescence properties of the mixed-metal organic framework may change in the presence of acetone, for example, the emission intensity may increase or decrease, and/or the colour of the emitted light may change upon exposure of the mixed-metal organic framework to the volatile organic compound of interest.
  • the emission is decreased (quenched) in the presence of the acetone.
  • the property is fluorescence and measuring a property of the mixed-metal organic framework comprises measuring the emission spectrum of the mixed-metal organic framework.
  • the mixed-metal organic framework may be any mixed-metal organic framework as described herein.
  • the mixed-metal organic framework comprises a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions of a substituted or unsubstituted biphenyl dicarboxylic acid, or ions of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • aromatic carboxylate ion linkers preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (isophthalate).
  • the aromatic carboxylate ion linker is benzene-1 , 4-dicarboxylate (terephthalate).
  • the method may comprise contacting the sample of breath with a mixed-metal organic framework comprising zinc ions, silver ions and terephthalate ions, and measuring a property of the mixed-metal organic framework to determine the level of acetone in the sample.
  • the property is fluorescence and measuring a property of the mixed-metal organic framework comprises measuring the emission spectrum of the metal organic framework. Generally the emission of the mixed-metal organic framework is decreased (i.e. is quenched) in the presence of acetone.
  • the metal organic framework or mixed-metal organic framework as described herein may be thermochromic and/or mechanochromic.
  • Thermochromic materials change colour in response to a change in temperature.
  • Mechanochromic materials change colour in response to stress in the solid state, for instance stress caused by mechanical grinding, crushing and milling; by friction and rubbing, or by high pressure or sonification.
  • the metal organic framework or mixed-metal organic framework may be a photoluminescent and/or electroluminescent material.
  • electroluminescent material refers to a material that accepts charge, both electrons and holes, which subsequently recombine and emit light.
  • photoluminescent material refers to a material that is able to absorb photons and undergo photoexcitation, then emit photons.
  • the metal organic framework or mixed-metal organic framework as described herein exhibits photoluminescence.
  • the photoluminescence of the metal organic framework or mixed-metal organic framework may change in response to a change in temperature, or in response to mechanical stress.
  • the metal organic framework or mixed-metal organic framework may be a luminescent thermochromic metal organic framework or mixed-metal organic framework.
  • the metal organic framework or mixed-metal organic framework may be a luminescent mechanochromic metal organic framework or mixed-metal organic framework. These properties lead to various applications of the metal organic framework or mixed-metal organic framework as described herein in devices that are able to respond to a stimulus and produce a detectable signal.
  • thermochromic or mechanochromic may easily be established by method known to the skilled person. For instance, the material could be heated up or cooled down under a ultraviolet lamp and observed for changes in photoluminescence.
  • the photoluminescent properties of the material can be established in the absence of mechanical stress, then mechanical stress may be induced by, for example, compressing the material into a pellet and observing whether or not the photoluminescent properties change.
  • the invention provides a device comprising a metal organic framework or mixed-metal organic framework as described herein, wherein the device is selected from a light emitting device, a photoluminescent device, a electroluminescent device, a luminescent thermometer, a mechanical force sensor, a chemical sensor, a motion sensing system, a data storage device, security paper, optical memory devices and vibration damage detectors.
  • a light emitting device a photoluminescent device, a electroluminescent device, a luminescent thermometer, a mechanical force sensor, a chemical sensor, a motion sensing system, a data storage device, security paper, optical memory devices and vibration damage detectors.
  • the metal organic framework or mixed-metal organic framework may have useful applications a thermometer, preferably in a luminescent thermometer.
  • the invention therefore also provides a luminescent thermometer comprising a thermochromic metal organic framework or mixed-metal organic framework, wherein the metal organic framework or mixed-metal organic framework is as described herein.
  • the skilled person would be well aware of how to construct a luminescent thermometer which comprises the metal organic framework or mixed-metal organic frameworks described herein.
  • a luminescent thermometer device may readily be constructed by disposing the metal organic framework or mixed-metal organic framework on a substrate, then irradiating the metal organic framework or mixed-metal organic framework on the substrate with an LED.
  • the emission of the metal organic framework or mixed-metal organic framework may be filtered using a long- pass filter and then measured using a photodiode. The emission will be translated into a numerical signal displayed in a small screen to display the temperature.
  • the luminescent thermometer may be self-calibrated.
  • the metal organic framework or mixed-metal organic framework in the luminescent thermometer may be any metal organic framework or mixed-metal organic framework as described herein.
  • the metal organic framework or mixed-metal organic framework in the luminescent thermometer comprises a silver ion and/or a lead ion and one or more organic linkers.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions of a substituted or unsubstituted biphenyl dicarboxylic acid, or ions of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • aromatic carboxylate ion linkers preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (phthalate).
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate).
  • metal organic framework or mixed-metal organic framework typically comprises silver ions and/or lead ions and terephthalate ions.
  • the luminescent thermometer comprises a thermochromic metal organic framework comprising one or more metal ions that are silver ions or lead ions and one or more organic linkers which are terephthalate ions.
  • the metal organic framework or mixed-metal organic framework may have useful applications a force sensor.
  • the invention therefore also provides a mechanical force sensor comprising a mechanochromic metal organic framework or mixed-metal organic framework, wherein the metal organic framework or mixed-metal organic framework is as described herein.
  • the mechanical force sensor may comprise a film of the metal organic framework or mixed-metal organic framework disposed on a solid substrate.
  • one side of the film of the metal organic framework or mixed-metal organic framework is in contact with the substrate, either directly or via an intermediate layer.
  • the solid substrate may act as a surface against which the film of the metal organic framework or mixed-metal organic framework can be compressed, for instance in response to a compressive force or pressure.
  • the response of the metal organic framework or mixed-metal organic framework may be determined by irradiating the metal organic framework or mixed-metal organic framework on the substrate with an LED.
  • the emission of the metal organic framework or mixed-metal organic framework may be filtered using a long-pass filter and then measured using a photodiode. Changes in emission intensity may then be used to locate areas of the substrate where a force has been applied and/or to quantify the magnitude of the force applied.
  • the metal organic framework or mixed-metal organic framework in the mechanical force sensor may be any metal organic framework or mixed-metal organic framework as described herein.
  • the metal organic framework or mixed-metal organic framework in the mechanical force sensor comprises a silver ion and/or a lead ion and one or more organic linkers.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions of a substituted or unsubstituted biphenyl dicarboxylic acid, or ions of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • aromatic carboxylate ion linkers preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3-dicarboxylate (phthalate).
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate).
  • metal organic framework or mixed-metal organic framework typically comprises silver ions and/or lead ions and terephthalate ions.
  • the mechanical force sensor comprises a mechanochromic metal organic framework comprising one or more metal ions that are silver ions or lead ions and one or more organic linkers which are terephthalate ions.
  • the invention also provides a chemical sensor comprising a metal organic framework or mixed- metal organic framework as described herein.
  • the metal organic framework or mixed- metal organic framework exhibits a change in photoluminescence when exposed to a particular chemical.
  • the photoluminescence properties of the mixed-metal organic framework may change in the presence of the chemical of interest.
  • the emission intensity may increase or decrease, and/or the colour of the emitted light may change upon exposure of the metal organic framework or mixed-metal organic framework to the chemical of interest.
  • the metal organic frameworks or mixed-metal organic frameworks of the present invention are stable in water.
  • the chemical sensor may be suitable for sensing the presence of a chemical in an aqueous sample.
  • the chemical sensor comprising the metal organic framework or mixed-metal organic framework may be suitable for sensing a chemical selected from the group consisting of chemical pollutants and drugs in an aqueous sample.
  • the invention also provides antibacterial material comprising a metal organic framework or a mixed-metal organic framework as described herein.
  • the antibacterial material comprises a metal organic framework or mixed-metal organic framework comprising silver ions.
  • the antibacterial material comprises a metal organic framework or mixed-metal organic framework comprising an imidazole-based linker, preferably an imidazolate linker of formula (I) or an imidazole linker of formula (II), as described herein.
  • the antibacterial material may comprise a metal organic framework or mixed-metal organic framework comprising silver ions and an imidazole-based linker, preferably an imidazolate linker of formula (I) or an imidazole linker of formula (II), as described herein.
  • the invention also provides a device comprising a metal organic framework or a mixed-metal organic framework, as defined herein, wherein the device is an optoelectronic device.
  • the device is an electroluminescent device.
  • the device is an electroluminescent device comprising an electroluminescent layer, wherein the electroluminescent layer comprises the metal organic framework or mixed-metal organic framework.
  • the device comprises one or more additional components selected from the group consisting of a p-type layer, an n-type layer and one or more electrodes.
  • the device comprises a first electrode and a second electrode.
  • the first and second electrode may comprise any suitable electrically conductive material.
  • the first electrode typically comprises one or more metals.
  • the first electrode typically comprises a metal selected from silver, gold, copper, aluminium, platinum, palladium, or tungsten, preferably aluminium.
  • the second electrode typically comprises a transparent conducting oxide.
  • the second electrode typically comprises a transparent conducting oxide and the second electrode typically comprises one or more metals.
  • the transparent conducting oxide typically comprises fluorine- doped tin oxide (FTO), indium tin oxide (ITO) or aluminium-doped zinc oxide (AZO), and typically ITO.
  • the device comprises an n-type layer and a p-type layer.
  • the n-type layer comprises an organic electron-transporting material.
  • the n-type layer comprises 2-(4- tert-Butylphenyl) -5 -(4-biphenylyl) -1,3,4 -oxadiazole (p-PBD) .
  • the p-type layer comprises a organic hole-transporting material.
  • the p-type layer comprises poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
  • the electroluminescent layer comprises the metal organic framework or mixed-metal organic framework dispersed in a conducting polymer matrix, preferably wherein the conducting polymer matrix comprises poly(9-vinylcarbazole) (PVK) polymer.
  • the conducting polymer matrix comprises poly(9-vinylcarbazole) (PVK) polymer.
  • the metal organic framework or mixed-metal organic framework in the electroluminescent device comprises silver ions and/or lead ions and one or more organic linkers.
  • the one or more organic linkers are selected from aromatic carboxylate ion linkers, preferably from ions of a substituted or unsubstituted benzene dicarboxylic acid, ions of a substituted or unsubstituted benzene tricarboxylic acid, ions of a substituted or unsubstituted naphthalene dicarboxylic acid, ions of a substituted or unsubstituted biphenyl dicarboxylic acid, or ions of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate) or benzene 1,3- dicarboxylate (phthalate).
  • the aromatic carboxylate ion linker is benzene-1, 4- dicarboxylate (terephthalate).
  • the metal organic framework or mixed-metal organic framework typically comprises silver ions and/or lead ions and terephthalate ions.
  • the electroluminescent comprises a metal organic framework comprising one or more metal ions that are silver ions or lead ions and one or more organic linkers which are terephthalate ions.
  • the device may comprise a first electrode, an n-type layer, an electroluminescent layer comprising the metal organic framework or mixed-metal organic framework, a p-type layer and a second electrode.
  • the first electrode is typically in contact with the n-type layer.
  • the second electrode is typically in contact with the p-type layer. Therefore, the electroluminescent device may comprise the following layers in the following order:
  • electroluminescent layer comprising the metal organic framework or mixed-metal organic framework as defined herein;
  • V a second electrode as defined herein.
  • the electroluminescent device may comprise the following layers in the following order:
  • n-type layer comprising p-PBD
  • electroluminescent layer comprising the metal organic framework or mixed-metal organic framework as defined herein dispersed in conducting polymer matrix, preferably wherein the conducting polymer matrix comprises poly(9- vinylcarbazole) (PVK) polymer;
  • the crystalline structure, morphology and luminescent properties of OX-2 MOFs were characterized by a combination of X-ray, spectroscopy and microscopy techniques.
  • Powder X-ray diffraction (PXRD) experiments were carried out in a Rigaku Smart Lab diffractometer with a Cu K ⁇ source (1.541 ⁇ ). The diffraction data were collected using 0.01° step size, 1° min-1 and at 2 ⁇ angle ranging from 2° to 32°.
  • Field emission scanning electron microscopy (FESEM) and energy- dispersive X-ray (EDX) images and spectra were obtained using the Carl Zeiss Merlin equipped with a high-resolution field emission gun.
  • Micrographs were attained under high vacuum with an accelerating voltage of 10 kV and in secondary electron imaging mode.
  • FTIR spectra were recorded on a NicoletTM iSTM 10 FTIR Spectrometer. The FTIR spectrum of each sample was collected 3 times and then averaged.
  • Steady-state fluorescence spectra, excitation-emission maps, luminescence quantum yields and time-resolved emission decays were recorded using a FS5 spectrofluorometer (Edinburgh Instruments) equipped with different modules for each specific experiment (i.e. integrating sphere for quantum yield, heated sample module to measure the emission of powders at different temperatures and a standard solid holder for powder experiments).
  • the samples were pumped with a 365-nm centred pulsed diode laser.
  • the instrumental response function (IRF, ⁇ 800 ps) was used to deconvolute the emission decays.
  • the decays were fitted to a multiexponential function and the quality of the fit was estimated by the ⁇ 2, which was always below 1.2.
  • the PXRD patterns of all synthesized OX-2 MOFs (in methanol (OX-2 m ), in methanol but using different ratio of organic linker and metal salt, 1 :2 BDC:AgNO 3 (OX-2 m:1/2 ), in DMF (OX-2 DMF ) and in water (OX-2 w )) are very similar, showing no significant changes neither in the peak intensity nor in the peak position, and resembling to a previously reported Ag-carboxylate coordination polymer.
  • the molecular formula of this Ag network corresponds to [Ag(BDC) 1/2 ] n and the crystalline structure reveals a 3D framework with short Ag-Ag distances (2.901 ⁇ ).
  • binuclear Ag 2 (BDC) 2 may be considered as the building units, which are connected head-to-tail giving place to 1D chains, which in turn are linked by Ag-O bonds with other BDC linkers to form the 2D wave -like layers. Finally, those layers are interweaved one each other to result in a 3D framework (Sun, D et al., Syntheses and characterizations of a series of silver- carboxylate polymers, Inorganica Chimica Acta 2004, 357 (4), 991-1001).
  • the FTIR spectra of the different OX-2 MOFs depicted in Figure 7 show no remarkable differences apart from a broad band at ⁇ 1700 cm -1 for OX-2 DMF which can be attributed to u ⁇ o of remaining DMF molecules in OX-2 MOF (Shastri, A et al., Spectroscopy ofN,N-dimethylformamide in the VUV andIR regions: Experimental and computational studies, J. Chem. Phys. 2017, 147 (22), 224305).
  • the FTIR spectra of all OX-2 exhibit bands at -1520, 1360, 1300, 1150, 1090, 1010, 890, 820 and 740 cm -1 .
  • the bands at 1520 and 1360 cm -1 can be ascribed to asymmetric and symmetric stretching vibrations of the carboxylic groups of the BDC linker coordinated to the Ag metal centre (Biemmi, E et al., Synthesis and characterization of a new metal organic framework structure with a 2D porous system: (H2NEt2)2[Zn3(BDC)4] •3DEF. Solid State Sciences 2006, 8 (3), 363-370). Moreover, the lack of bands in the region between 1750-1680 cm -1 indicates a complete deprotonation of terephthalic acid as expected.
  • OX-2 m , OX-2 DMF and OX-2 w MOFs are very white powders (see photos in Figure 1), however, under UV irradiation there is a significant difference in the emission intensity of these powders, that decreases from the OX-2 synthesized in water > methanol > DMF. On the other side, OX-2 m:1/2 presents a brownish colour under daylight (see photo in Figure 1).
  • OX- 2m 1/2, OX2 m and OX-2 DMF , where some appreciable changes were perceived. While the FESEM images of OX-2 w ( Figures 2A-B), OX2 m and OX-2 DMF ( Figure 8) show very homogenous distribution of elongated nanoplates (height 60-100 nm, Figure 9), OX-2 m:1/2 presents three different morphologies: i) elongated nanoplates, ii) aggregation of a second type of nanoplates creating a kind of “flower” shaped crystals, and iii) a kind of micro-sized columns ( Figures 2 C-D).
  • the excitation-emission maps of OX-2 m , OX-2 m:1/2 , OX-2 DMF and OX-2 w reveal no very significant differences, with all of them showing a vibrationally resolved emission, having maxima located at 485, 520 and 560 nm that correspond to an excitation maximum of ⁇ 330 nm ( Figure 3).
  • OX-2 m:1/2 is composed by elongated nanoplates and “flowers” and “column” shaped crystals.
  • the elongated nanoplates of OX-2 m:1/2 are similar to those observed for OX-2 w and it is assumed that those are the emissive ones.
  • the flowers presents different proportion of Ag/C and the column shaped crystals are composed only by C and O atoms.
  • the band at ⁇ 520-nm was assigned to a metal- to-ligand charge -transfer transition (MLCT), whereas the ⁇ 485-nm one was attributed to intra- ligand emission as it was more or less similar to a weak emission at 466 nm previously reported for terephthalic acid (Liu., Four silver-containing coordination polymers based on bis (imidazole) ligands, Journal of Coordination Chemistry 2008, 61 (22), 3583-3593).
  • this assumption is not fully supported by the following facts: i) the intra-ligand emission of BDC is 20-nm blue shifted (466-nm) compared to the observed in OX-2 (485-nm).
  • the intra-ligand BDC emission band is much broader (FWHM ⁇ 3250cm -1 ) (Fun et al., A three-dimensional network coordination polymer , (terephthalato)(pyridine)cadmium, with blue fluorescent emission, Journal of the Chemical Society, Dalton Transactions 1999, (12), 1915-1916) that the band at 485-nm observed for OX-2 MOFs (FWHM ⁇ 1050cm -1 , deconvoluted from OX-2 emission), whose narrowness matches better with a vibrationally-resolved structure, and iii) it is possible to anticipate that the three vibrationally-resolved bands response in a comparable way to external stimuli.
  • LMCT ligand-to-metal charge transfer
  • LMCT ligand-metal-metal charge transfer
  • M-M Metal-Metal
  • this scalable approach produces identical OX-2 w to that synthesized in a small scale, as shown by the comparable PXRD ( Figure 12) and luminescence properties with the expected vibrationally-resolved bands at 485, 520 and 560nm ( Figure 13) and a ⁇ Exc( 330nm) value of ⁇ 60 ⁇ 3%.
  • the potential applicability of any material has to satisfy certain described conditions, hence, the chemical stability of this OX-2 in water and at ambient conditions has been also tested.
  • OX-2 w was soaked in water for 1, 4 , 8 and 21 days and then dried at 80°C under vacuum for 2 hours.
  • OX-2 MOF has proved to be a very robust material with no remarkable changes neither in its crystalline structure nor in its photo luminescence properties upon soaked in water for a period of 21 days and after being exposed to ambient conditions in the lab (day light, ⁇ 40% humidity, solvent vapours, etc) for a total of 70 days.
  • OX-2 MOF also exhibits an excellent luminescent response to mechanical compression (pelletizing the powder) and to changes in the temperature.
  • the thermochromic behaviour showed a linear response of the emission intensity with the temperature, and those changes are very reproducible and repeatable.
  • OX-2 MOF also behaves as a good electroluminescent material as their excited state mechanism is based on LMCT and LMMCT processes. Therefore, this work shed light on the easy synthesis of this new luminescent nanomaterial, remarking the outstanding potential of OX-2 to be integrated in multiple real-word technologies.
  • the synthesis of the material consists of two steps: i) synthesis of OX-1 MOF (already reported); and ii) substitution of Zn atoms by Ag in OX-1 MOF leading to a new mixed-metal MOF (MM- MOF) material.
  • OX-1 MOF 250 mg
  • 1 mmol (169 mg) of AgNO 3 powders 250 mg
  • a few micro liters of water from 50 to 500 ⁇ L
  • the initial OX-1 MOF which is non-emissive is converted to a highly photoluminescent mixed-metal organic framework. After that, the sample was dried at 90°C overnight.
  • the luminescent response of the mixed-metal organic framework to different VOCs was carried out by adding 2 mg of the mixed-metal organic framework material to 4 mL of each solvent.
  • the mixed-metal organic framework suspensions were sonicated for 10 minutes and then their emission was collected by using a FS-5 spectrofluorometer.
  • the emission spectra of the mixed-metal organic framework in the presence of different VOCs remain almost unaltered, however in presence of acetone, the emission is completely supressed.
  • MOF metal organic framework
  • the one or more metal ions comprise one or more metal ions of group 9, 10, 11, 12 or 14 of the periodic table, preferably wherein the one or more metal ions comprise one or more ions selected from Ag, Au, Cu, Cd, Ir, Pt, ,Pd and Pb ions .
  • the one or more organic linkers are selected from carboxylate ion linkers and imidazole-based linkers, and preferably from aromatic carboxylate ion linkers and imidazole-based linkers.
  • the aromatic carboxylate ion linker is selected from an ion of a substituted or unsubstituted benzene dicarboxylic acid, an ion of a substituted or unsubstituted benzene tricarboxylic acid, an ion of a substituted or unsubstituted naphthalene dicarboxylic acid, an ion of a substituted or unsubstituted biphenyl dicarboxylic acid, or an ion of a substituted or unsubstituted 1,3,5-triphenylbenzene tricarboxylic acid.
  • R and R’ are selected fromH, OH, NH2, CH3, CN, NO2, F, Cl, Br, I, -OC3H5, OC7H7. 10. The process according to any one of clauses 5 to 9 wherein the aromatic carboxylate ion linker is benzene-1, 4-dicarboxylate (terephthalate).
  • imidazole-based linker is an imidazolate linker of formula (I) or an imidazole linker of formula (II):
  • R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, C1-10 alkyl, C2 10 alkenyl, C2-10 alkynyl, cyano, and halogen, provided that R2 and R3 or R6 and R7 may be joined so as to form a substituted or unsubstituted ring, preferably wherein R2 and R3 or R6 and R7 are joined to form a 5 or 6-membered ring, optionally wherein the ring comprises 1, 2 or 3 heteroatoms selected from O, N and S, and provided that any one of R1 to R7 may be a hydrocarbon linker bonded to a further substituted or unsubstituted imidazole or imidazolate ring.
  • metal organic framework further comprises water of crystallization.
  • a metal organic framework comprising one or more metal ions and one or more organic linkers, wherein the metal organic framework is obtainable by a process which comprises contacting the one or more metal ions with the one or more organic linkers in the presence of water to form a precipitate of the metal organic framework, wherein the process is performed at a temperature that does not exceed 50°C, optionally wherein the process is as further defined in any one of claims 2 to 20.
  • a metal organic framework comprising a silver ion and one or more organic linkers, wherein the metal organic framework has a photo luminescence quantum yield of greater than 50%.
  • a device comprising a metal organic framework as defined in any one of clauses 21 to 27, wherein the device is selected from a light emitting device, a photoluminescent device, a electroluminescent device, a luminescent thermometer, a mechanical force sensor, a chemical sensor, a motion sensing system, a data storage device, security paper, optical memory devices and vibration damage detectors.
  • thermometer 29 A luminescent thermometer comprising a thermochromic metal organic framework, wherein the metal organic framework is as defined in any one of clauses 21 to 27.
  • a mechanical force sensor comprising a mechanochromic metal organic framework, wherein the metal organic framework is as defined in any one of clauses 21 to 27.
  • a chemical sensor comprising a metal organic framework as defined in any one of clauses 21 to 27.
  • a device comprising a metal organic framework as defined in any one of clauses 21 to 27, wherein the device is an optoelectronic device, preferably wherein the device is an electroluminescent device.
  • the device is an electroluminescent device comprising an electroluminescent layer, wherein the electroluminescent layer comprises the metal organic framework, preferably wherein the electroluminescent layer comprises the metal organic framework dispersed in a conducting polymer matrix, preferably wherein the conducting polymer matrix comprises poly(9-vinylcarbazole) (PVK) polymer.
  • the electroluminescent layer comprises the metal organic framework
  • the electroluminescent layer comprises the metal organic framework dispersed in a conducting polymer matrix, preferably wherein the conducting polymer matrix comprises poly(9-vinylcarbazole) (PVK) polymer.
  • PVK poly(9-vinylcarbazole)
  • a process for producing a mixed-metal organic framework wherein the mixed- metal organic framework comprises a first metal ion, a second metal ion and one or more organic linkers, wherein the process comprises contacting a metal organic framework comprising a first metal ion and the one or more organic linkers with a compound comprising the second metal ion in the presence of a polar protic solvent to form the mixed-metal organic framework, preferably where the polar protic solvent is water.
  • first and second metal ions are selected from group 9, 10, 11, 12 or 14 metal ions, preferably wherein the first and second metal ions are selected from Zn, Ag, Au, Cu, Cd, Ir, Pt, Pd or Pb ions, more preferably wherein the first metal ion is a Zn ion and the second metal ion is an Ag ion.
  • the compound comprising the second metal ion is a salt of the second metal ion, preferably wherein the salt of the second metal ion is a salt of formula MXn, wherein M represents the second metal ion; X is an anion selected from halide, nitrate or CH3COO-; and wherein n depends on the charge of the second metal ion, M, and the charge of the anion, X.
  • a mixed-metal organic framework comprising a first metal ion, a second metal ion and one or more organic linkers, wherein the first metal ion is a zinc ion; and the second metal ion is a silver ion.
  • a device comprising a mixed-metal organic framework as defined in any one of clauses 40 to 42, wherein the device is a chemical sensor.
  • a method for detecting the presence of a volatile organic compound comprising contacting a mixed-metal organic framework as defined in any one of clauses 40 to 42 with the volatile organic compound and measuring a property of the mixed-metal organic framework.
  • the method according to clause 44 wherein the property is fluorescence and measuring a property of the mixed-metal organic framework comprises measuring the emission spectrum of the metal organic framework.
  • a method for analysing a sample of breath from a subject, wherein the subject has, or is suspected of having, diabetes comprising contacting the sample of breath with a mixed-metal organic framework as defined in any one of clauses 40 to 42, and measuring a property of the mixed-metal organic framework to determine the level of acetone in the sample.
  • a device comprising a mixed-metal organic framework as defined in any one of clauses 40 to 42, wherein the device is selected from a light emitting device, a photoluminescent device, a luminescent thermometer, a mechanical force sensor, a chemical sensor, a motion sensing system, a data storage device, security paper, optical memory devices and vibration damage detectors.
  • thermometer comprising a thermochromic mixed-metal organic framework, wherein the mixed-metal organic framework is as defined in any one of clauses 40 to 42.
  • a mechanical force sensor comprising a mechanochromic mixed-metal organic framework, wherein the mixed-metal organic framework is as defined in any one of clauses 40 to 42.
  • a device comprising a mixed-metal organic framework as claimed in any one of clauses 40 to 42, wherein the device is an optoelectronic device, preferably wherein the device is an electroluminescent device.

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Abstract

L'invention concerne un procédé de production d'une structure organométallique, la structure organométallique comprenant un ou plusieurs ions métalliques et un ou plusieurs lieurs organiques, le procédé comprenant la mise en contact du ou des ions métalliques avec le ou les lieurs organiques en présence d'eau pour former un précipité de la structure organométallique, le procédé étant effectué à une température qui ne dépasse pas 50 °C.
PCT/GB2021/050495 2020-02-28 2021-02-26 Procédé de synthèse d'une structure organométallique et structure organométallique WO2021171033A1 (fr)

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CN115304878A (zh) * 2022-08-10 2022-11-08 景德镇陶瓷大学 一种具有热致可逆变色性质的Cu-BTC/高分子聚合物复合膜及其制备方法和产品
CN115651651A (zh) * 2022-11-10 2023-01-31 昆明理工大学 一种金属有机聚合物黄色发光材料及其制备方法
CN115960376A (zh) * 2022-12-08 2023-04-14 福建农林大学 一种基于琼脂的抗菌复合薄膜制备方法及其应用
CN116217950A (zh) * 2022-12-15 2023-06-06 天津大学 一种金属有机框架共晶材料及其在光催化降解中的应用
CN116390607A (zh) * 2023-03-17 2023-07-04 天津大学 一种提高晶体管光电性能的方法

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CN115304878A (zh) * 2022-08-10 2022-11-08 景德镇陶瓷大学 一种具有热致可逆变色性质的Cu-BTC/高分子聚合物复合膜及其制备方法和产品
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CN115304878B (zh) * 2022-08-10 2023-05-26 景德镇陶瓷大学 一种具有热致可逆变色性质的Cu-BTC/高分子聚合物复合膜及其制备方法和产品
CN115651651A (zh) * 2022-11-10 2023-01-31 昆明理工大学 一种金属有机聚合物黄色发光材料及其制备方法
CN115651651B (zh) * 2022-11-10 2023-10-13 昆明理工大学 一种金属有机聚合物黄色发光材料及其制备方法
CN115960376A (zh) * 2022-12-08 2023-04-14 福建农林大学 一种基于琼脂的抗菌复合薄膜制备方法及其应用
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CN116217950B (zh) * 2022-12-15 2023-08-11 天津大学 一种金属有机框架共晶材料及其在光催化降解中的应用
CN116390607A (zh) * 2023-03-17 2023-07-04 天津大学 一种提高晶体管光电性能的方法
CN116390607B (zh) * 2023-03-17 2023-10-20 天津大学 一种提高晶体管光电性能的方法

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