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 arbejde blev støttet af National Natural Science Foundation of China (21471037), Guangdong naturvidenskab midler til fremtrædende unge forskere (15ZK0307), videnskab og teknologi planlægger projektet af Guangdong-provinsen (2017A050506051), og den Forskningsråd tilskud af HKSAR [GRF 11303414].

Forsigtig: Kontakt venligst alle relevante leverandørbrugsanvisninger før brug. Methyl disulfid og natrium thiomethoxide er stærkt ildelugtende og bør håndteres i et stinkskab. Natrium metal er meget reaktive og kræver særlige sikkerhedsforanstaltninger mod potentielle brand og eksplosion farer. Ud over brugen af et stinkskab, bør personlige værnemidler (sikkerhedsbriller, handsker, laboratoriekittel, fuld længde bukser og lukket tå sko) være korrekt ansat. Dele af følgende procedurer indebærer standard, lu...

<ol>
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(15), 2333-2334 (1994).</li><li>Sakamoto, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=pi-Conjugated+Trinuclear+Group-9+Metalladithiolenes+with+a+Triphenylene+Backbone.">pi-Conjugated Trinuclear Group-9 Metalladithiolenes with a Triphenylene Backbone.</a> Inorg Chem. 52 (13), 7411-7416 (2013).</li><li>Testaferri, L., Tiecco, M., Tingoli, M., Chianelli, D., Montanucci, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simple+Syntheses+of+Aryl+Alkyl+Thioethers+and+of+Aromatic+Thiols+from+Unactivated+Aryl+Halides+and+Efficient+Methods+for+Selective+Dealkylation+of+Aryl+Alkyl+Ethers+and+Thioethers.">Simple Syntheses of Aryl Alkyl Thioethers and of Aromatic Thiols from Unactivated Aryl Halides and Efficient Methods for Selective Dealkylation of Aryl Alkyl Ethers and Thioethers.</a> Synthesis. (9), 751-755 (1983).</li><li>Testaferri, L., Tingoli, M., Tiecco, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reactions+of+polychlorobenzenes+with+alkanethiol+anions+in+HMPA.+A+simple,+high-yield+synthesis+of+poly(alkylthio)benzenes.">Reactions of polychlorobenzenes with alkanethiol anions in HMPA. A simple, high-yield synthesis of poly(alkylthio)benzenes.</a> J Org Chem. 45 (22), 4376-4380 (1980).</li><li>Tiecco, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+dealkylations+of+aryl+alkyl+ethers,+thioethers,+and+selenoethers.">Selective dealkylations of aryl alkyl ethers, thioethers, and selenoethers.</a> Synthesis. 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Reaktionen mellem gruppen bromo og thiomethoxide anion tilsyneladende produceret først methyl thioether, som derefter blev demethylated af den overskydende thiomethoxide at give thiolate anion produkt. For at sikre komplet konvertering til den ønskede thiolate anion (især for en polybromide substrat som HBT), energisk betingelserne for forlænget opvarmning (fx, 240 ° C over 48 h) med et stort overskud af natrium thiomethoxide (f.eks.over tre gange modermærker af grupperne bromo) er afgørende. Kv?...

Der er i øjeblikket stor interesse i at ansætte stærke, polariserbare metal-svovl (fx., metal-thiolate) links til at konstruere åbne rammer materialer med forøget electrocatalytic og ledende egenskaber1,2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10. ud over at fremme elektronisk kommunikation og transport i udvidet tilstand, blød og kovalente metal-svovl links også give bedre stabilitet for applikationer i vandige miljøer. Blandt svovl-udstyret byggestenene, symmetrisk, multidentate polycykliske aromatiske byggesten som 2,3,6,7,10,11-triphenylene hexathiol (HTT)9,11,12,13 , 14 ikke kun levere yderst polariserbare π-elektroner, men også tilbyde forskellige fordele i forhold til ramme design og syntese. Først, den stive og symmetrisk triphenylene kerne, sammenholdt med chelaterende dithiolene grupper af HTT, tjener til at låse i metal ioner i regelmæssig limning motiver, forenkle de strukturelle forudsigelse af fremtidige netværk7, 15. sammen med de stive og åben geometri af svovl linker, rammer strukturer med betydelige porøsitet funktioner kan ofte opnås i fast tilstand.
En stor udfordring i at samle thiol-udstyret metal orangic framework (MOF) materialer er forankret i syntesen af økologisk linker molekyler. I en klassisk protokol måtte gruppen thiol afledes fra gruppen fenol ved hjælp af Newman-Kwart omordning af den O- aryl thiocarbamatbaserede forløber16,17,18. Denne fremgangsmåde indebærer imidlertid omfattende forberedende skridt for phenol forløber molekyle samt potentielle komplikationer af en høj temperatur faste fase transformation. En anden måde at gøre dithioler udnytter reduktiv dealkylation af thioethers under de barske betingelser for eksempelvis natrium metal i flydende ammoniak19,20,21,22, og er ikke kompatibel med carboxyl og mange andre donor funktioner til netværk konstruktion.
Til sammenligning, den protokol, der præsenteres her har flere fordele: sikkerhed, bekvemmelighed, omkostningseffektiviteten og kompatibiliteten med andre funktionelle grupper (fx., carbonitrile og pyridinyl). Ved energisk opvarmning generelt billig aromatiske Halogenid (fx., hexabromotriphenylene) og thiomethoxide anion, thiolate anion blev genereret (via methyl thioether mellemproduktet) og derefter acylated at give stabile og nem at håndtere thioester produkt-alt i én gryde.
Vi vil også beskrive en procedure for at udnytte thioester molekyler som den maskerede form for thiol linkers giver adgang til en single-krystallinsk halvledende og porøse metal-dithiolene netværk. I modsætning til de meget reaktive fritstående dithioler, som er tilbøjelige til at nedbryde og komplicere krystalliseringen af metal-thiolate åbne rammer, thioester let kan kløves (fx., af NaOH eller ethylendiamin) i situ at give den thiol arter, der betjener mindske reaktion mellem mercaptan enheder og metal-Centre og dermed forbedre krystalliseringen.
Denne protokol til at forberede thiol/thioester har ikke været meget anvendt af andre grupper for det nye felt af metal-svovl rammer, selvom nukleofil dealkylations af alkyl aryl thioethers af thiolate anioner er allerede blevet godt dokumenteret af økologisk kemikere23,24,25,26. Ved fremvisning af denne effektive syntetiske metode til thioesters og deres anvendelse for at lette krystalliseringen af metal-svovl netværk, vi ønsker at fremme yderligere bestræbelser på at slå bro over den intellektuelle og praktiske kløft mellem syntetisk organisk kemi og solid state kemi, for at hjælpe den hurtig og sund udvikling af 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 præsenterer en metode til at forberede thioester molekyler som den maskerede form for thiol linkers og deres udnyttelse for at få adgang til en halvledende og porøse metal-dithiolene netværk i den stærkt bestilte krystallinsk enhedsstat. I modsætning til de meget reaktive fritstående dithioler, som er tilbøjelige til at nedbryde og komplicere krystalliseringen af metal-thiolate åbne rammer, thioester reagerer i stedet for at give thiol arter, der tjener til at afbøde reaktionen mellem den mercaptan enheder og metal-centre, og at forbedre krystallisering derfor. Specifikt, thioester blev syntetiseret i et en-pot procedure: en aromatisk bromid (hexabromotriphenylene) reagerede med overskydende natrium thiomethoxide energisk betingelser først danne thioether mellemproduktet. Thioether blev derefter demethylated af den overskydende thiomethoxide at give thiolate anion, der var acylated at danne thioester produkt. Thioester var bekvemt renset ved standard kolonne kromatografi, og derefter bruges direkte i ramme syntese, hvori NaOH og ethylendiamin tjener til at vende tilbage i situ thioester til thiol linker til montering af Single-krystallinsk Pb (II)-dithiolene netværk. Sammenlignet med andre metoder til thiol syntese (fx., ved at holde alkyl thioether ved hjælp af natrium metal og flydende ammoniak), thioester syntese her bruger enkle betingelser og økonomisk reagenser. Thioester produkt er desuden stabil og kan nemt håndteres og opbevares. Vigtigere, i modsætning til generiske vanskeligheden ved at få adgang til krystallinsk metal-thiolate åbne rammer, vise vi at bruger thioester in situ dannelsen af thiol linker i høj grad forbedrer crystallinity af det solid-state produkt. Vi agter at tilskynde bredere forskningsindsats på de teknologisk vigtige metal-svovl rammer ved at afsløre de syntetiske protokol for thioester samt de krystallinske rammer solid.

IR-spektrum af HVaTT molekyle (indsamlet af KBr pellet metode) har sin stærkeste absorption på 1.700 cm-1, i overensstemmelse med carbonyl udspænding af thioester funktionelle gruppe. 1H-NMR spektret af HVaTT (400 MHz, CDCl3) afslører en singlet på δ 8.47 fra de aromatiske brintatomer, sammen med 4 multiplets fra alifatiske protoner: δ 8.47 (s, 6 H, CHAr), 2,75-2.72 (t, J = 7.4, 12 H, CH2), 1,81-1,77 (m, 12 H, CH2), 1,...

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 præsenterer vi et en-pot, overgang-metal-fri syntese af dithioler og thioesters fra aromatiske halogenider og natrium thiomethoxide, efterfulgt af udarbejdelsen af enkelte krystaller af en metal-dithiolene netværk ved hjælp af thiol arter genereret in situ fra den mere stabil og tractable thioester.

Syntese af en Thiol byggesten for krystallisering af halvledende Gyroidal Metal-svovl rammer

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

Fremstilling og anvendelse af Samarium Diiodide (SMI<sub&gt; 2</sub&gt;) I Organic Synthesis: Den mekanistiske rolle HMPA og Ni (II) salte i Samarium Barbier Reaction

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 oprensning af Iodoaziridines Inddragelse kvantitativ udvælgelse af det optimale stationære fase til 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 Eksfoliering af Discotic Zirconium Fosfater fås Kolloid Flydende Krystaller

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 af programmerbare Main-kæde Liquid-krystallinske Elastomerer hjælp af en to-trins Thiol-acrylat Reaktion

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 af Cd-fri InP / ZnS Quantum Dots Velegnet til 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-1 som en heterogen katalysator til syntese af 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 Separation ved selektiv krystallisation 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 af en Vandopløseligt Metal-Organic Complex Array

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

Elektroforetisk krystallisering af ultratynde højtydende Metal-økologiske rammer 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

Fast-fase syntese af [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 ...