Denne forskningen ble støttet av Basic Science Research Program gjennom National Research Foundation of Korea (NRF) finansiert av departementet for vitenskap og IKT (NRF-2022R1A2C1009706).

Reagensene som kreves for å forberede MOFs og ligandene er oppført i materialfortegnelsen.
1. Sette opp prosessen for postsyntetisk ligandutveksling (PSE)
<ol><li>Tørk de presyntetiserte UiO-66 MOF-ene helt under vakuum for å fjerne eventuelle uomsatte metallsalter og ligander i porene, og gjenværende løsemiddelrester over natten. MERK: Se tilleggsfil 1 for synteseprosedyren til UiO-66 MOF.</li>
	<li>Forbered funksjonaliserte ligander, H2 BDC-triazol ogH2BDC-tetrazol (se tilleggsfil 1 for fremstillingsprosessen; Tilleggsfigur 1 og tilleggsfigur 2 for karakterisering) i isolert tilstand og helt tørr under vakuum over natten.</li>
	<li>Lag en vandig løsning på 4% kaliumhydroksid (KOH) ved å oppløse kaliumhydroksid i avionisert vann.</li>
	<li>PSE-prosessen skal utføres i hetteglass med 20 ml scintillasjon med polypropylenlokk (PP) (se materialfortegnelse).</li>
	<li>Mål H 2 BDC-triazol (23,3 mg, 0,1 mmol) eller H2BDC-tetrazol(23,4 mg, 0,1 mmol) og sett inn i scintillasjonshetteglasset.</li>
	<li>Oppløs H2BDC-liganden i vandig løsning. Bruk en glasspipette til å overføre 1,0 ml av den 4 % vandige KOH-oppløsningen til scintillasjonshetteglasset med BDC-triazol eller BDC-tetrazol. FORSIKTIG: Den vandig oppløsning på 4% KOH er svært grunnleggende. Unngå alle former for kontakt og bruk personlig verneutstyr.</li>
	<li>Sonikere blandingen til alle faste stoffer er fullstendig oppløst.</li>
	<li>Nøytraliser løsningen til pH 7. Bruk en glasspipette til å overføre 1 M saltsyre (HCl) vandig oppløsning under omrøring i hetteglasset med dikarboksylat til pH 7 er nådd. Mål pH enten med pH-papir (og fargen) eller en pH-måler. MERK: Det er avgjørende å opprettholde en pH på 7 under utvekslingsprosessen, siden MOFer vanligvis er ustabile under grunnleggende forhold (>pH 7), og BDC-liganden ikke er løselig under sure forhold (<pH 7). Omtrent 1,5 ml 1 M HCl vandig oppløsning er nødvendig for å nøytralisere BDC-triazol eller BDC-tetrazolholdig oppløsning.</li>
	<li>Legg MOFs til dikarboksylatoppløsningen og inkuber. Tilsett UiO-66 MOF (33 mg, 0,02 mmol) til scintillasjonshetteglasset med pH 7-oppløsning. MERK: Ved pH 7 er UiO-66 MOF-partikler ikke løselige i vann, noe som resulterer i suspensjon i vann.</li>
	<li>Inkuber hetteglasset med scintillasjon som inneholder MOF og ligand i en shaker ved 120 rpm og ved romtemperatur i 24 timer. MERK: Omrøring kan brukes som et alternativ til shaker-inkubasjon for PSE-prosessen. Imidlertid bør forsiktighet utvises, siden fysisk kontakt mellom den magnetiske omrøringsstangen og MOF-er kan føre til sprekkdannelse eller brudd på MOF-partiklene.</li>
</ol>2. Isolering av utvekslet MOF og vaskeprosess
<ol><li>Etter inkubering, isoler det faste MOF fra blandingen ved sentrifugering (1,166 x g, 5 min, romtemperatur).</li>
	<li>Tilsett fersk metanol (10 ml) til det oppnådde faste MOF og rist blandingen for å danne en heterogen blanding for å oppløse de gjenværende uutvekslede BDC-ligander.</li>
	<li>Isoler det faste stoffet som ble isolert ved sentrifugering (1,166 x g, 5 min, romtemperatur).</li>
	<li>Gjenta trinn 2.2-2.3 to ganger til i totalt tre vaskesykluser.</li>
	<li>Tørk det utskiftede MOF-faste stoffet helt under vakuum over natten etter siste vask.</li>
</ol>3. Karakterisering av MOF ved pulverrøntgendiffraksjon (PXRD)
<ol><li>Overfør ca. 10 mg av det utskiftede faste MOF-stoffet til en PXRD-prøveholder (se materialfortegnelsen).</li>
	<li>Plasser prøveholderen i diffraktometeret.</li>
	<li>Samle PXRD-mønsteret (figur 2) i 2θ-området fra 5° til 30°.</li>
	<li>Sammenlign innhentede data med overordnet UiO-66 MOF og simulert mønster.</li>
</ol>4. Karakterisering av MOF ved kjernemagnetisk resonans (NMR) etter fordøyelse
<ol><li>Overfør ca. 30 mg av det utskiftede MOF-faste stoffet til et nytt 4 ml hetteglass.</li>
	<li>Bruk en mikropipette til å overføre 400 mikroliter DMSO-d 6 til MOF-prøven.</li>
	<li>Bruk en mikropipette til å overføre 200 μL 4,14 M NH4F/D2O-oppløsning til en DMSO-d 6-suspensjon av MOF-pulver. MERK: En vandig oppløsning på ca. 40 % HF kan brukes i stedet forNH4F/D2O-oppløsningen. I dette tilfellet observeres en signifikant H2O-topp i NMR. Imidlertid er klarere fordøyelse mulig ved HF-fordøyelse. FORSIKTIG: HF er svært giftig for kroppen og sentralnervesystemet. Alle former for kontakt bør unngås, arbeid skal utføres i avtrekkshette, og personlig verneutstyr skal brukes.</li>
	<li>Sonikere den heterogene blandingen i 30 minutter til MOF er oppløst i dimetylsulfoksydet (DMSO)-D2O-blandetløsningsmiddel etter fordøyelsen.</li>
	<li>Fjern eventuelle gjenværende uoppløselige faste stoffer ved å filtrere oppløsningen gjennom et sprøytefilter av polyvinylidendifluorid (PVDF) (Φ 13 mm, 0,45 μm pore; se materialfortegnelse) mens det overføres fra 4 ml hetteglasset til et NMR-rør.</li>
	<li>Plasser NMR-røret i NMR-maskinen. Samle inn NMR-data (figur 3).</li>
</ol>

Triazol og tetrazol funksjonaliserte Zr-MOFs syntese og karakterisering

<ol>
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PSE-prosessen med funksjonaliserte BDC-ligander mot Zr-baserte UiO-66 MOFs er en enkel og allsidig metode for å oppnå MOFs med kjemiske koder. PSE-prosessen utføres best i vandige medier, og krever det første trinnet med å løse liganden i et vandig medium. Ved bruk av presyntetisert BDC med funksjonelle grupper anbefales direkte oppløsning i et basisk løsningsmiddel, for eksempel en 4% KOH vandig løsning. Alternativt kan natrium- eller kaliumsalt av benzen-1,4-dikarboksylat brukes. Nøytralisering til pH 7 er kr...

Metallorganiske rammer (MOF) er tredimensjonale porøse materialer som dannes gjennom koordinasjonsbindinger mellom metallklynger og multi-topic organiske ligander. MOF-er har fått betydelig oppmerksomhet på grunn av deres permanente porøsitet, lave tetthet og evne til å knytte organiske og uorganiske komponenter, noe som muliggjør forskjellige applikasjoner 1,2. Videre tilbyr det store spekteret av metallnoder og stagorganiske linkere MOF-er teoretisk ubegrensede strukturelle kombinasjoner. Selv med identiske rammestrukturer kan MOFs fysiske og kjemiske egenskaper modifiseres gjennom ligandfunksjonalisering med kjemiske koder. Denne modifikasjonsprosessen tilbyr en lovende rute for å skreddersy egenskapene til MOF-er for spesifikke applikasjoner 3,4,5,6,7,8,9.
Både prefunksjonalisering av ligander før MOF-syntese og postsyntetisk modifikasjon (PSM) av MOFs har blitt brukt til å introdusere og/eller modifisere funksjonelle grupper i MOF-ligander10,11. Spesielt har kovalente PSM-er blitt grundig studert for å introdusere nye funksjonelle grupper og generere en rekke MOF-er med forskjellige funksjoner12,13,14. For eksempel kan UiO-66-NH2 konverteres til amidfunksjonaliserte UiO-66-AM med forskjellige kjedelengder (fra korteste acetamid til lengste n-heksylamid) gjennom acyleringsreaksjoner med passende acylhalogenider (som acetylklorid eller n-heksanoylklorid)15,16. Denne tilnærmingen demonstrerer allsidigheten til kovalente PSM-er for å introdusere spesifikke funksjonelle grupper på MOF-ligander, og baner vei for et bredt spekter av applikasjoner.
I tillegg til kovalente PSM-er er postsyntetisk ligandutveksling (PSE) en lovende strategi for å modifisere MOF-er (figur 1). Siden MOFs er sammensatt av koordinasjonsbindinger mellom metaller og ligander (som karboksylater), kan disse koordinasjonsbindingene erstattes med eksterne ligander fra en løsning. Eksponering av MOFs til en løsning som inneholder ønsket ligand med kjemiske koder kan inkorporeres i MOFs via PSE 17,18,19,20,21,22. Siden PSE-prosessen akselereres av eksistensen av koordinative løsningsmidler, kalles fenomenet også solvent-assistert ligandutveksling (SALE)23,24. Denne tilnærmingen tilbyr en fleksibel og enkel metode for å funksjonalisere MOF-er med et bredt spekter av eksterne ligander, noe som muliggjør et bredt spekter av applikasjoner 25,26,27,28,29.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65619/65619fig01.jpg"> Figur 1 Syntese av triazol og tetrazolfunksjonaliserte H2BDC-ligander og fremstilling av triazol- og tetrazolfunksjonalisert UiO-66 MOF gjennom PSE. <a href="https://www.jove.com/files/ftp_upload/65619/65619fig01large.jpg" target="_blank">Klikk her for å se en større versjon av denne figuren.</a>
Fremdriften av PSE-prosessen kan styres ved å justere ligandforholdet, utvekslingstemperaturen og tiden. Spesielt kan romtemperatur PSE brukes til å oppnå funksjonaliserte MOF-er ved å bytte ligander fra en løsning til MOF-faste stoffer20. PSE-strategien er spesielt nyttig for å introdusere både termisk ustabile funksjonelle grupper (som azidogrupper) og koordinative funksjonelle grupper (som fenolgrupper) i MOF-strukturer18. I tillegg har PSE-strategien blitt brukt på ulike MOFer med metall- og koordinasjonsbindingsvariasjoner. Denne utvekslingen er en universell prosess i kjemien til MOFs30,31,32. I denne studien presenterer vi en detaljert protokoll for PSE for å oppnå funksjonaliserte MOF-er fra uberørte, ikke-funksjonaliserte MOF-er, og vi gir en karakteriseringsstrategi for å bekrefte vellykket funksjonalisering av MOF-ene. Denne metoden demonstrerer allsidigheten og bekvemmeligheten til PSE for å modifisere MOF-er med forskjellige funksjonelle grupper.
Tetrazolholdig benzen-1,4-dikarboksylsyre (H2BDC-tetrazol)33 og triazolholdig benzen-1,4-dikarboksylsyre (H2BDC-triazol) syntetiseres som målligander og benyttes i PSE hos UiO-66 MOFs for å oppnå nye, koordinasjonsfrie, triazolholdige MOFs. Både triazoler og tetrazoler har sure N-H-protoner på sine heterocykliske ringer og kan koordinere med metallkationer, noe som muliggjør bruk i konstruksjon av MOFs34,35. Det er imidlertid begrensede studier på inkorporering av koordinasjonsfrie tetrazoler og triazoler i MOFs og relaterte strukturer. Ved triazolfunksjonaliserte Zr-MOF ble UiO-68 type MOFs undersøkt fotofysiske egenskaper gjennom direkte solvotermisk syntese med benzotriazolfunksjonalitet36. For tetrazolfunksjonaliserte Zr-MOFs ble den blandede direkte syntesen benyttet33. Disse heterosyklusfunksjonaliserte MOF-ene kan gi potensielle koordineringssteder i MOF-porene for katalyse, selektivt molekylært opptak ved bindingsaffinitet og energirelaterte applikasjoner, for eksempel protonledning i brenselceller.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>2-Bromoterephthalic acid</td>
			<td>BLD Pharm</td>
			<td>BD5695</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Azidotrimethylsilane</td>
			<td>Simga Aldrich</td>
			<td>155071</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Bis(triphenylphosphine)palladium(II) dichloride</td>
			<td>TCI</td>
			<td>B1667</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Copper(I) cyanide</td>
			<td>Alfa-Aesar</td>
			<td>12135</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Copper(I) iodide</td>
			<td>Acros organics</td>
			<td>20150</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Digital Orbital Shaker</td>
			<td>Daihan Scientific</td>
			<td>SHO-1D</td>
			<td>PSE</td>
		</tr>
		<tr>
			<td>Formic Acid</td>
			<td>Daejung chemical</td>
			<td>F0195</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Hybrid LC/Q-TOF system</td>
			<td>Bruker BioSciences</td>
			<td>maXis 4G</td>
			<td>HR-MS</td>
		</tr>
		<tr>
			<td>Lithum hydroxide monohydrate</td>
			<td>Daejung chemical</td>
			<td>5087-4405</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Magnesium sulfate</td>
			<td>Samchun chemical</td>
			<td>M1807</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Methyl alcohol</td>
			<td>Daejung chemical</td>
			<td>M0584</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>N,N-Dimethylformamide</td>
			<td>Daejung chemical</td>
			<td>D0552</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Nuclear Magnetic Resonance Spectrometer-500 MHz</td>
			<td>Bruker</td>
			<td>AVANCE 500MHz</td>
			<td>NMR</td>
		</tr>
		<tr>
			<td>Polypropylene cap (22 mm, Cork-Backed Foil Lined)</td>
			<td>Sungho Korea</td>
			<td>22-200</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Potassium cyanide</td>
			<td>Alfa-Aesar</td>
			<td>L13273</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>PVDF Synringe filter (13 mm, 0.45 &#181;m)</td>
			<td>LK Lab Korea</td>
			<td>F14-61-363</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Scintillation vial (20 mL, borosilicate glass)</td>
			<td>Sungho Korea</td>
			<td>74504-20</td>
			<td>material for digestion</td>
		</tr>
		<tr>
			<td>Sodium azide&#160;</td>
			<td>TCI</td>
			<td>S0489</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Sodium bicarbonate</td>
			<td>Samchun chemical</td>
			<td>S0343</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Tetrabutylammonium fluoride (1 M THF solution)</td>
			<td>Acros organics</td>
			<td>20195</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine</td>
			<td>TCI</td>
			<td>T0424</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triethylamine hydrochloride</td>
			<td>Daejung chemical</td>
			<td>8628-4405</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
		<tr>
			<td>Trimethylsilyl-acetylene</td>
			<td>Alfa-Aesar</td>
			<td>A12856</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>Triphenylphosphine</td>
			<td>TCI</td>
			<td>T0519</td>
			<td>reagent for BDC-Triazole</td>
		</tr>
		<tr>
			<td>X RAY DIFFRACTOMETER SYSTEM</td>
			<td>Rigaku</td>
			<td>MiniFlex 600</td>
			<td>PXRD</td>
		</tr>
		<tr>
			<td>Zirconium(IV) chloride</td>
			<td>Alfa-Aesar</td>
			<td>12104</td>
			<td>reagent for BDC-Tetrazole</td>
		</tr>
	</tbody>
</table>

synthesis of triazole and tetrazole-functionalized zr-based metal-organic frameworks through post-synthetic ligand exchange

Metallorganiske rammer (MOF) er en klasse av porøse materialer som dannes gjennom koordinasjonsbindinger mellom metallklynger og organiske ligander. Gitt deres koordinative natur, kan de organiske ligandene og stagrammen lett fjernes fra MOF og / eller byttes ut med andre koordinative molekyler. Ved å introdusere målligander til MOF-holdige løsninger, kan funksjonaliserte MOF-er oppnås med nye kjemiske koder via en prosess som kalles postsyntetisk ligandutveksling (PSE). PSE er en enkel og praktisk tilnærming som muliggjør utarbeidelse av et bredt spekter av MOFer med nye kjemiske koder via en likevektsprosess med faste løsninger. Videre kan PSE utføres ved romtemperatur, noe som tillater inkorporering av termisk ustabile ligander i MOF. I dette arbeidet demonstrerer vi praktisk bruk av PSE ved å bruke heterosykliske triazol- og tetrazolholdige ligander for å funksjonalisere en Zr-basert MOF (UiO-66; UiO = Universitetet i Oslo). Etter fordøyelsen karakteriseres de funksjonaliserte MOF-ene via forskjellige teknikker, inkludert pulverrøntgendiffraksjon og kjernemagnetisk resonansspektroskopi.

Metal-organic frameworks (MOFs) are three-dimensional porous materials that are formed through coordination bonds between metal clusters and multi-topic organic ligands. MOFs have garnered significant attention due to their permanent porosity, low density, and ability to associate organic and inorganic components, which enables diverse applications1,2. Moreover, the vast range of metal nodes and strut organic linkers offer MOFs theoretically unlimited structural combinations. Even with identical framework structures, MOFs&#39; physical and chemical properties can be modified through ligand functionalization with chemical tags. This modification process offers a promising route to tailor the properties of MOFs for specific applications3,4,5,6,7,8,9.
Both the pre-functionalization of ligands prior to MOF synthesis and post-synthetic modification (PSM) of MOFs have been employed to introduce and/or modify functional groups in MOF ligands10,11. In particular, covalent PSMs have been extensively studied to introduce new functional groups and generate a range of MOFs with diverse functionalities12,13,14. For instance, UiO-66-NH2 can be converted to amide-functionalized UiO-66-AMs with different chain lengths (ranging from the shortest acetamide to the longest n-hexyl amide) through acylation reactions with appropriate acyl halides (such as acetyl chloride or n-hexanoyl chloride)15,16. This approach demonstrates the versatility of covalent PSMs to introduce specific functional groups onto MOF ligands, paving the way for a broad range of applications.
In addition to covalent PSMs, post-synthetic ligand exchange (PSE) is a promising strategy for modifying MOFs (Figure 1). Since MOFs are composed of coordination bonds between metals and ligands (such as carboxylates), these coordination bonds can be replaced with external ligands from a solution. Exposing MOFs to a solution containing the desired ligand with chemical tags can be incorporated into the MOFs via PSE17,18,19,20,21,22. Since the PSE process is accelerated by the existence of coordinative solvents, the phenomenon is also called solvent-assisted ligand exchange (SALE)23,24. This approach offers a flexible and facile method for functionalizing MOFs with a wide range of external ligands, enabling a broad spectrum of applications25,26,27,28,29.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/65619/65619fig01.jpg" /> 
Figure 1: Synthesis of triazole and tetrazole-functionalized H2BDC ligands and preparation of triazole- and tetrazole-functionalized UiO-66 MOF through PSE. <a href="https://www.jove.com/files/ftp_upload/65619/65619fig01large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
The progress of the PSE process can be controlled by adjusting the ligand ratio, exchange temperature, and time. Notably, room temperature PSE can be employed to obtain functionalized MOFs by exchanging ligands from a solution into MOF solids20. The PSE strategy is particularly useful for introducing both thermally unstable functional groups (such as azido groups) and coordinative functional groups (such as phenol groups) into MOF structures18. In addition, the PSE strategy has been applied to various MOFs with metal and coordination bond variations. This exchange is a universal process in the chemistry of MOFs30,31,32. In this study, we present a detailed protocol for PSE to obtain functionalized MOFs from pristine, non-functionalized MOFs, and we provide a characterization strategy to confirm successful functionalization of the MOFs. This method demonstrates the versatility and convenience of PSE for modifying MOFs with diverse functional groups.
Tetrazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Tetrazole)33, and triazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Triazole) are synthesized as target ligands and utilized in the PSE of UiO-66 MOFs to obtain novel, coordination-free, triazole-containing MOFs. Both triazoles and tetrazoles possess acidic N-H protons on their heterocyclic rings and can coordinate with metal cations, thus enabling their use in constructing MOFs34,35. However, there are limited studies on incorporating coordination-free tetrazoles and triazoles into MOFs and related structures. In case of triazole-functionalized Zr-MOFs, UiO-68 type MOFs were investigated to photophysical properties through direct solvothermal synthesis with benzotriazole functionalities36. For tetrazole-functionalized Zr-MOFs, the mixed direct synthesis was employed33. These heterocycle-functionalized MOFs could provide potential coordinating sites in MOF pores for catalysis, selective molecular uptake by binding affinity, and energy-related applications, such as proton conduction in fuel cells.

Forfatter Spotlight: Funksjonalisering av metallorganiske rammeverk: fremskritt, utfordringer og kraften til postsyntetisk ligandutveksling 

Syntese av triazol og tetrazol-funksjonaliserte Zr-baserte metallorganiske rammer gjennom postsyntetisk ligandutveksling

Our main research topic is functionalizing the porous metal-organic frameworks, MOFs, with interesting functional groups through various techniques. This study is focused on heterocycle installation in MOFs. PSE, post-synthetic ligand exchange is the main technique in this work.The ligand with target functional group could be installed in presynthesized MOFS throughout the solid-solution exchange process. Especially, some of the unstable ligands and ligands with coordinating groups could be efficiently incorporated into MOFs through the PSE techniques. Both triazole and tetrazole functional groups have multiple coordinating nitrogen grooves.Therefore, there is competition for coordination between metal carboxylate and metal triazolate or tetrazolate. The incorporation ratio of target ligands is easily controlled in the PSE process and multiple targets could be installed in a single MOF through this approach.

Den vellykkede syntesen av utvekslede UiO-66 MOF, UiO-66-Triazol og UiO-66-Tetrazol produserte fargeløse mikrokrystallinske faste stoffer. Både H2 BDC-triazol ogH2BDC-tetrazolligander viste også en fargeløs fast tilstand. Standardmetoden som ble brukt for å bestemme suksessen til utvekslingen innebar å måle PXRD-mønstrene og sammenligne krystalliniteten til prøven med uberørt UiO-66 MOF. Figur 2 viser PXRD-mønstrene for utvekslet UiO-66-Triazol og UiO-66-Tetr...

Watch this Scientific Journal Video about Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange at JoVE.com

Postsyntetisk ligandutveksling (PSE) er et allsidig og kraftig verktøy for å installere funksjonelle grupper i metallorganiske rammer (MOF). Eksponering av MOFs til løsninger som inneholder triazol- og tetrazolfunksjonaliserte ligander kan inkorporere disse heterosykliske delene i Zr-MOFs gjennom PSE-prosesser.

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. ...

Vårt hovedtema er å funksjonalisere de porøse metall-organiske rammeverkene, MOFs, med interessante funksjonelle grupper gjennom ulike teknikker. Denne studien er fokusert på heterosyklusinstallasjon i MOFs. PSE, postsyntetisk ligandutveksling er hovedteknikken i dette arbeidet.Liganden med målfunksjonell gruppe kan installeres i presyntetiserte MOFS gjennom hele fastløsningsutvekslingsprosessen. Spesielt kan noen av de ustabile ligandene og ligandene med koordinerende grupper effektivt innlemmes i MOFs gjennom PSE-teknikkene. Både triazol- og tetrazolfunksjonelle grupper har flere koordinerende nitrogenspor.Derfor er det konkurranse om koordinering mellom metallkarboksylat og metalltriazolat eller tetrazolat. Inkorporeringsforholdet mellom målligander styres enkelt i PSE-prosessen, og flere mål kan installeres i en enkelt MOF gjennom denne tilnærmingen.

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Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

1.8K Views.  Chungbuk National University. Our main research topic is functionalizing the porous metal-organic frameworks, MOFs, with interesting functional groups through various techniques. This study is focused on heterocycle installation in MOFs. PSE, post-synthetic ligand exchange is the main technique in this work.The ligand with target functional group could be installed in presynthesized MOFS throughout the solid-solution exchange process. Especially, some of the unstable ligands and ligands with coordinating groups cou...

Video: Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange 

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. Given their coordinative nature, the organic ligands and strut framework can be readily removed from the MOF and/or exchanged with other coordinative molecules. By introducing target ligands to MOF-containing solutions, functionalized MOFs can be obtained with new chemical tags via a process called post-synthetic ligand exchange (PSE). PSE is a straightforward and practical approach that enables the preparation of a wide range of MOFs with new chemical tags via a solid-solution equilibrium process. Furthermore, PSE can be performed at room temperature, allowing the incorporation of thermally unstable ligands into MOFs. In this work, we demonstrate the practicality of PSE by using heterocyclic triazole- and tetrazole-containing ligands to functionalize a Zr-based MOF (UiO-66; UiO = University of Oslo). After digestion, the functionalized MOFs are characterized via various techniques, including powder X-ray diffraction and nuclear magnetic resonance spectroscopy.

Post-synthetic ligand exchange (PSE) is a versatile and powerful tool for installing functional groups into metal-organic frameworks (MOFs). Exposing MOFs to solutions containing triazole- and tetrazole-functionalized ligands can incorporate these heterocyclic moieties into Zr-MOFs through PSE processes.

Setting up the Post-synthetic Ligand Exchange (PSE) Process, Exchanged MOF Isolation and Washing Process

Begin by measuring 23.3 milligrams of H2BDC triazole and place it into the scintillation vial. To dissolve the H2BDC ligand in the aqueous solution, transfer 1.0 milliliters of the 4%potassium hydroxide solution into the vial using a glass pipette. Next, sonicate the mixture until all solids completely dissolve.Add one molar hydrochloric acid solution into the decarboxylate-containing vial and stir until a pH of 7 is reached. Add 33 milligrams of UiO-66 MOF to the scintillation vial. Then incubate the vial with the MOF and ligand at room temperature and 120 RPM in a shaker for 24 hours.Next, isolate the solid MOF from the mixture by centrifugation at 1166g for five minutes. at room temperature. Add 10 milliliters of fresh methanol to the obtained solid MOF and shake the vial, creating a heterogeneous mixture to dissolve any remaining unchanged BDC ligands.Isolate the solid once again by centrifuging the mixture at 1166g for five minutes at room temperature and dry it.

Sette opp PSE-prosessen (Post-synthetic Ligand Exchange), utvekslet MOF-isolasjons- og vaskeprosess

Characterization of the MOF by Powder X-Ray Diffraction (PXRD) and Nuclear Magnetic Resonance (NMR) After Digestion

Transfer approximately 10 milligrams of the MOF solid exchanged with UiO-66-Triazole to a powder X-ray diffraction sample holder. Place the sample holder in the diffractometer, and collect the powder X-ray diffraction pattern. To begin NMR characterization, transfer around 30 milligrams of the exchanged MOF solid to a fresh four milliliter vial.Then move 400 microliters of DMSO-d6 to the MOF sample using a micro pipette. Transfer 200 microliters of 4.14 molar ammonium fluoride deuterium oxide solution to a DMSO-d6 suspension of MOF powder using a micro pipette. Sonicate the heterogeneous mixture for 30 minutes until the MOF is dissolved in the dimethyl sulfoxide deuterium oxide mixed solvent after digestion.Once done, remove any remaining insoluble solids by filtering the solution through a polyvinylidene difluoride syringe filter while transferring it from the four milliliter vial to a nuclear magnetic resonance tube. To determine the success of the exchange, powder X-ray diffraction patterns were measured and compared to pristine UiO-66 MOF for crystallinity. The position of reflection peaks, relative intensity, and broadness in the powder X-ray diffraction patterns of exchanged UiO-66-Triazole and UiO-66-Tetrazole matched with pristine UiO-66 MOFs, indicating that the ligand exchange did not impact the framework structure.The exchange ratios were determined by comparing the integration of nonfunctionalized BDC and BDC-Triazole or BDC-Tetrazole. The exchange ratios for Triazole and Tetrazole were found to be 33%and 30%respectively from post synthetic ligand exchange analysis.