Name: synthesis of a thiol building block for the crystallization of a semiconducting gyroidal metal-sulfur framework
Uploaded: 2018-04-09T13:00:00
Description: Watch this Scientific Journal Video about Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework at JoVE.com

Dette arbeidet ble støttet av National Natural Science Foundation i Kina (21471037), Guangdong naturvitenskap midler for fremragende unge forskere (15ZK0307), vitenskap og teknologi planlegging prosjektet av Guangdongprovinsen (2017A050506051), og Forskning tilskudd Rådet for HKSAR [GRF 11303414].

Forsiktig: Se alle relevante sikkerhetsdatablader før bruk. Methyl disulfide og natrium thiomethoxide er sterkt malodorous og skal håndteres i avtrekksvifte. Natrium er svært reaktive og krever spesielle sikkerhetsforanstaltninger mot potensielle brann og eksplosjonsfarer. I tillegg til avtrekksvifte, skal personlig verneutstyr (vernebriller, hansker, laboratoriefrakk, full lengde bukser og lukket-toe sko) bli riktig ansatt. Deler av følgende innebære standard, luft-fri behandling teknikker.
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<ol>
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Reaksjonen gruppen bromo og thiomethoxide anion angivelig produsert først metyl-thioether, som ble deretter demethylated av den overskytende thiomethoxide å levere thiolate anion produktet. For å sikre full konvertering til ønsket thiolate anion (spesielt for en polybromide substrat som HBT), energisk betingelsene for langvarig oppvarming (f.eks, 240 ° C over 48 timer) med en stor overskudd av natrium thiomethoxide (f.eks, over tre ganger muldvarpene av bromo grupper) er avgjørende. Nitrogen besky...

Det er nå stor interesse for å ansette sterk, polarizable metall-svovel (f.eks., metall-thiolate) linker for å konstruere åpne ramme materiale med forbedret electrocatalytic og ledende egenskaper1,2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10. i tillegg til fremme elektronisk samhandling og transport i utvidet tilstand, myk og kovalente metall-svovel koblingene også formidle bedre stabilitet for programmer i vandig miljøer. Blant svovel utstyrte byggesteiner, symmetrisk, multidentate Polysykliske aromatiske byggeklosser som 2,3,6,7,10,11-triphenylene, hexathiol (HTT),9,,11,,12,,13 , 14 ikke bare levere svært polarizable π-elektroner, men tilbyr også forskjellige fordeler når det gjelder rammeverk design og syntese. Først tjener stive og symmetrisk triphenylene kjernen, sammen med chelaterande dithiolene grupper av HTT, til å låse i metall ioner i vanlige bånd motiver, forenkle strukturelle prediksjon av potensielle nettverk7, 15. sammen med den stive og åpne geometrien av svovel linker, framework strukturer med betydelig porøsitet funksjoner kan ofte oppnås i til solid state.
En hovedutfordring i sammenstillingen thiol utstyrt metall orangic rammeverk (MOF) materialer er forankret i syntesen av organisk koblingsfunksjonalitet molekyler. I en klassisk protokoll måtte gruppen thiol være avledet fra gruppen fenol bruker Newman-Kwart omorganisering av O- aryl thiocarbamate forløper16,17,18. Denne tilnærmingen innebærer imidlertid omfattende preparative trinnene for fenol Forløperen molekylet, samt mulige komplikasjoner av en høy temperatur solid fase transformasjon. En annen måte å thiols benytter reductive dealkylation av thioethers under harde forhold av, for eksempel natrium metall i flytende ammoniakk19,20,21,22, og ikke kompatibel med carboxyl og mange andre donor funksjoner for nettverk konstruksjon.
Sammenligning av protokollen presenteres her har flere fordeler: sikkerhet, brukervennlighet, kostnadseffektivitet og kompatibilitet med andre funksjonelle grupper (f.eks., carbonitrile og pyridinyl). Av kraftig oppvarming vanligvis billig aromatiske metallhalid (f.eks., hexabromotriphenylene) og thiomethoxide anion, thiolate anion ble generert (via methyl thioether mellomliggende product) og deretter acylated å gi stabile og lett å håndtere thioester produkt-alt i en pott.
Vi vil også beskriver en prosedyre for å utnytte thioester molekyler som den maskerte thiol linkers for tilgang til en én-krystallinske semiconducting og porøs metall-dithiolene nettverk. I motsetning til de svært reaktive stående thiols, som pleier å oppløse og komplisere krystallisering av metall-thiolate åpne rammer, thioester kan være lett kløyvde (f.eks., NaOH eller ethylenediamine) i situ å gi den thiol arter, serverer å redusere reaksjonen mercaptan enhetene og metall sentrene, og dermed forbedre krystallisering.
Denne protokollen forberede thiol/thioester har ikke vært mye brukt av andre grupper for det nye feltet metall-svovel rammeverk, selv om nukleofil dealkylations av alkyl aryl thioethers av thiolate anioner allerede er godt dokumentert av organisk kjemikere23,24,25,26. Ved utstillingsvindu denne effektiv syntetisk metoden for thioesters og deres bruk for å tilrettelegge krystallisering av metall-svovel nettverk, vi ønsker å fremme ytterligere innsats for å bygge bro intellektuelle og praktisk skillet mellom syntetisk organisk kjemi og robust begrunne kjemi, for å hjelpe rask og sunn utvikling av porøse rammer.

<table border="0" cellpadding="0" cellspacing="0" width="850">
	<tbody>
		<tr height="22">
			<td height="22" style="height:22px;width:216px;">Bromine</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">7726-95-6</td>
			<td style="width:167px;">Highly toxic</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Triphenylene&#160;&#160;</td>
			<td style="width:348px;">HWRK Chem</td>
			<td style="width:119px;">HWG45510</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Iron powder</td>
			<td style="width:348px;">Sigma-Aldrich</td>
			<td style="width:119px;">12310</td>
			<td></td>
		</tr>
		<tr height="24">
			<td height="24" style="height:24px;width:216px;">Nitrobenzene</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">2934</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:216px;">Diethyl ether&#160;</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td style="width:119px;">48</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:216px;">Dichloromethane</td>
			<td style="width:348px;">DAMAO CHEMICAL REAGENT FACTORY</td>
			<td>3067</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Sodium metal</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">WM-NMS-54-25X-50G</td>
			<td>Air sensitive</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Tetrahydrofuran</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">315353</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Dimethyl disulfide</td>
			<td style="width:348px;">INTERNATIONAL LABORATORY USA</td>
			<td style="width:119px;">726415</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">1,3-Dimethyl-2-imadazolidinone</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">50483</td>
			<td>Dried over 4&#197; sieves</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Valeryl&#160; chloride</td>
			<td style="width:348px;">J&#38;K</td>
			<td style="width:119px;">99590</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Methanol</td>
			<td style="width:348px;">Guangzhou Chemical Reagent Factory</td>
			<td>2334</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sodium hydroxide</td>
			<td style="width:348px;">Guangzhou Chemical Reagent Factory</td>
			<td style="width:119px;">1588</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Ethylene diamine</td>
			<td style="width:348px;">Riedel-de Ha&#235;n</td>
			<td style="width:119px;">15070</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Lead acetate trihydrate</td>
			<td>PEKING CHEMICAL WORKE</td>
			<td style="width:119px;">861218</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of a thiol building block for the crystallization of a semiconducting gyroidal metal-sulfur framework

Vi presenterer en metode for å forberede thioester molekyler som maskert form av thiol linkers og utnyttelse for tilgang til en semiconducting og porøs metall-dithiolene nettverk i svært organisert enkelt Krystalinsk staten. I motsetning til de svært reaktive stående thiols, som pleier å oppløse og komplisere krystallisering av metall-thiolate åpne rammer, thioester reagerer i situ for å gi thiol arter, serverer å redusere reaksjonen på mercaptan enheter og metall sentrene, og forbedre krystallisering følgelig. Spesielt thioester ble syntetisert i en one-pot-prosedyre: en aromatiske bromide (hexabromotriphenylene) reagert med overflødig natrium thiomethoxide under energisk forhold til først thioether mellomliggende produktet. Thioether ble deretter demethylated av den overskytende thiomethoxide å gi den thiolate anion som var acylated til thioester produktet. Thioester var praktisk renset av artikkelen Ture, og deretter brukes direkte i rammeverket syntese, der NaOH og ethylenediamine tjene til å gå tilbake i situ thioester å thiol linker for montering av single-krystallinsk Pb (II)-dithiolene nettverk. Sammenlignet med andre metoder for thiol syntese (f.eks., av cleaving alkyl thioether med natrium metall og flytende ammoniakk), thioester syntese her bruker enkle betingelser og økonomisk reagenser. Videre thioester produktet er stabilt og kan enkelt håndteres og lagres. Enda viktigere, i motsetning til generisk vanskeligheter med tilgang til krystallinsk metall-thiolate åpne rammer, viser vi at med thioester in situ dannelsen av thiol linker forbedrer crystallinity av det SSD produkt. Vi ønsker å oppmuntre bredere forskningsinnsats på de teknologisk viktig metall-svovel rammene ved å avsløre syntetiske protokollen for thioester samt krystallinsk rammen solid.

IR spekteret av HVaTT molekyl (samlet av KBr pellet metoden) har sin sterkeste absorpsjon på 1700 cm-1, i samsvar med karbonyl strekking av funksjonsgruppen thioester. 1H-NMR spekter av HVaTT (400 MHz, CDCl3) avslører singlet på ses 8.47 fra de aromatiske bygget, sammen med 4 multiplets fra alifatisk protoner: ses 8.47 (s, 6 H, CHAr), 2,75-2.72 (t, J = 7.4, 12 H, lm-2), 1,81-1,77 (m, 12 H, CH2), 1,50-1.45 (dd, J =...

Watch this Scientific Journal Video about Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework at JoVE.com

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

Her presenterer vi en one-pot, overgang-metall-free syntese av thiols og thioesters fra aromatiske halides og natrium thiomethoxide, etterfulgt av utarbeidelse av enkelt krystaller av et metall-dithiolene nettverk med thiol arter generert i situ fra den mer stabil og tett thioester.

Syntese av en Thiol byggestein for krystallisering av en Semiconducting Gyroidal Metal-svovel-ramme

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

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Organic Chemistry

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Unit 1

Ethers, Epoxides, Sulfides

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Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

Forberedelse og bruk av Samarium Diiodide (SMI<sub&gt; 2</sub&gt;) I Organic Synthesis: det mekanistiske rolle HMPA og Ni (II) salter i Samarium Barbier Reaksjon

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

Syntese og rensing av Iodoaziridines Involvering Kvantitativ Valg av Optimal stasjonær fase for Kromatografi

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

Syntese og Peeling av Discotic Zirkonium Fosfater henter Kolloidalt Liquid Crystals

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction

Syntese av Programmerbar Hoved-kjeden Flytende-krystallinske Elastomers bruke et to-trinns Tiol-akrylat Reaction

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Syntese av Cd-fri INP / ZnS kvanteprikker Passer for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

HKUST-en som en heterogen katalysator for syntese av Vanillin

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

Sulfat Separasjon ved Selektiv Krystallisering med en Bis-iminoguanidinium Ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

Synthesis of a Water-soluble MetalÃƒÆ’Ã‚Â¢ÃƒÂ¢Ã¢â‚¬Å¡Ã‚Â¬ÃƒÂ¢Ã¢â€šÂ¬Ã…â€œOrganic Complex Array

Syntese av en vann-løselig metall-organisk kompleks rekke

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

Electrophoretic krystallisering av Ultrathin høyytelses Metal-organisk Framework membraner

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Solid-fase syntese av [4.4] Spirocyclic Oximes

A convenient synthetic route for spirocyclic heterocycles is well sought after due to the molecule&#39;s potential use in biological systems. By means of ...