이 작품 고유 영 학자 (15ZK0307), 과학 기술 계획 프로젝트의 광둥 성 (2017A050506051)에 대 한 국가 자연 과학 재단의 중국 (21471037), 광 동 자연과학 기금에 의해 지원 되었다 그리고 HKSAR [GRF 11303414]의 연구 보조금 위원회.

주의: 사용 하기 전에 모든 관련 물질 안전 데이터 시트를 참조 하십시오. 메 틸 아 황산 나트륨 thiomethoxide 강력 하 게 악취를 풍기는 고 증기 두건에서 처리 되어야 합니다. 나트륨 금속은 반응성이 매우 높은 이며 잠재적인 화재 및 폭발 위험에 대 한 특별 안전 조치. 연기 후드를 사용 하 여, 뿐만 아니라 개인 보호 장비 (안전 안경, 장갑, 실험실 코트, 전장 바지 및 폐쇄 발가락 신발) 제대로 고용 되어야 한다. 다음 절차의 일부 표준, 공기 없는 처리 기술 포함 한다.
1. 나트륨 Thiomethoxide (채널3SNa)의 준비
<ol><li>진공 가스 매니폴드를 200 mL Schlenk 플라스 크를 연결 합니다. 플라스 크를 철수 하 고 백필 N2 3 시간, 그런 플라스 크는 약간 긍정적인 N2 압력으로 가득. 참고: 채널3SNa를 준비 하는 유사한 방법에서 문학, 간략하게 언급 했다 하지만 더 자세한 절차27,28를 제공 했다.</li>
	<li>등유 석유 저수지에서 금속 나트륨의 블록을 꺼내. 종이 타월을 사용 하 여, 표면에 잔여 기름 닦아 내 고 칼을 사용 하 여 표면에 산화물 층을 다쳤어요. 신속 하 게 6.7 g 금속 나트륨 (0.29 mol)의 작은 조각으로 잘라 (예., 콩 크기에 대 한)와 작은 조각 N2의 카운터 흐름 아래 200 mL Schlenk 플라스 크에 즉시 전송. 즉시는 심장으로 플라스 크를 밀봉 하십시오. 참고: 공기에 노출을 줄이기 위해, 수 6.7 g의 금액에서 일부 유사 함께 나트륨을 잘라 한 THF와 디 메 틸 아 황산 나트륨 사용의 실제 금액에 따라 금액 조정.</li>
	<li>Schlenk 선에서 N2 보호 아래 정 맥을 통해 플라스 크에 무수, 답답한 THF의 80 mL를 전송. 디 메 틸 아 황산의 14.0 mL 철회 (0.158 두더지; N2와 함께 미리 제거) 주사기에 dropwise N2 보호 아래 플라스 크에 주입 하는 고. 주의: 디 메 틸 아 악취를 풍기 이며 증기 두건에서 처리 되어야 합니다.</li>
	<li>지상 유리 스 토퍼에 심장을 바꿉니다. 그리고 3 h 60 ° C에서 24 시간 실 온에서 반응 혼합물을 저 어. 참고: 반응 혼합물이 되었다 점성; 실 온에서 교 반 하면서 60 ° C까지가 열, 혼합 수 수 흔들 더 쉽고 따라서 완성으로 반응 속도.</li>
	<li>약 60 ° C에서 유지 하는 온도 함께 사용 하 여 stream의 N2 (0.2 L/min) 려 THF 용 매 및 초과 디 메 틸 아의 대부분을 건조 고체가 나타날 때까지. 콜드 트랩을 사용 하 여 (예., 아세톤/드라이 아이스) 유출에서 THF와 디 메 틸 아 수집 하.</li>
	<li>나머지 대피는 기름과 고체 혼합물 펌프 잔여 THF와 디 메 틸 아 황산 그리고 백필 제거 하려면 약 2 시간에 대 한 그것은 N2 라이트 옐로우 솔리드 (19.8 g, 97%)을 얻을. 어둠 속에서 질소 분위기에서 고체 제품 채널3SNa를 저장 합니다. 참고: 진공 오일 펌프를 보호 하기 위해 콜드 트랩 박동 하는 동안 사용 되어야 한다.</li>
</ol>2. 보호 thiol 링커로 2,3,6,7,10,11-hexakis (pentanoylthio) triphenylene (HVaTT)의 준비
<ol><li>채널3SNa 0.664 g 로드 (9.0 mmol) N2 의 카운터 흐름에서 50 mL Schlenk 플라스 크로 (즉., N2 보호 아래 진공 가스 매니폴드를 위에서 연결 된). 참고: 채널3SNa 공기에 민감한 이며 쉽게 물을 흡수. 공기에 노출을 최소화 하기 위해 수 있습니다 특정 금액을 신속 하 게 무게와 플라스 크에 그것을 추가 한 다음 그에 따라 다른 반응, 2,3,6,7,10,11-hexabromotriphenylene (HBT)의 수량을 조정. 주의: 단단한 채널3SNa 강한 냄새를가지고 하 고 증기 두건에서 처리 되어야 합니다.</li>
	<li>HBT의 0.216 g 추가 (0.30 mmol) N2및 물개는 심장으로 플라스 크의 카운터 흐름 아래 플라스 크에.</li>
	<li>Schlenk 선에서 N2 보호 아래 정 맥을 통해 플라스 크에 10 mL의 무수 및 무기 1, 3-디 메 틸-2-imidazolidinone (DMEU) 전송.</li>
	<li>일반 유리 스 토퍼 심장 대체 하 고 반응 혼합물을 저 어 소금 목욕 48 h N2에 대 한 240 ° C에가 열을 사용 하 여.</li>
	<li>TLC는 반응의 진행의 모니터링: N2를 사용 하 여 유리 dropper 반응 혼합물 (약 0.1 mL)의 작은 약 수를 철회 하 고 즉시 깔끔한 액체 샘플 플라스틱에서 valeroyl 염화 물 (약 0.1 mL)의 주입 microcentrifuge 유리병, 그리고 1 분;에 대 한 다음 흔들어 혼합물 즉시 회색-화이트 색상으로 혼 탁 한 설정 해야 합니다. 0.4 mL 이온 물과 에틸 아세테이트의 0.1 mL를 추가, 뚜껑 닫고 몇 초 동안 그것을 동요. 참고: 경우 반응 이미 완료, 거기 되지 않습니다 아무것도 물의 레이어와 에틸 아세테이트 사이 나타나는. 그렇지 않은 경우에 불용 성 물질이 두 레이어 사이 나타납니다.</li>
	<li>피펫으로 상단 부분을 밖으로 하 고 TLC 판 안보에 대 한 그것을 사용 하 여. 1:4 에틸 아세테이트/석유 에테르를 사용 하 여 TLC 판 개발. 완전 한 반응에 대 한 대상 분자 나타나 정기적으로 Rf 주위 자리 UV 램프에서 0.4 =.</li>
	<li>난방을 끄십시오 하 고 실내 온도에 냉각 소금 목욕에서 반응 플라스 크를 타고 얼음 목욕을 사용 하 여 0 ° c.까지 플라스 크를 냉각</li>
	<li>N2주사기 dropwise (기간 약 2 분) 플라스 크에 염화 물 valeroyl (12.6 mmol)의 1.5 mL를 주사. 2 헤 참고 0 ° C에서 계속 저 어: 부산물의 생성을 줄이는 데 도움이 됩니다 천천히, 그리고 낮은 온도에서 valeroyl 염화를 추가.</li>
	<li>얼음 물과 에틸 아세테이트 (3 30 mL)을 사용 하 여 추출 물 50 mL에 혼합물을 부 어. 다음 물 (6 60 mL), 무수 MgSO4, 이상 건조와 결합 된 유기 레이어를 세척 하 고 회전 하는 증발 기에 의해 휘발성을 제거.</li>
	<li>1시 10분을 사용 하 여 열 크로마토그래피에 의해 기름 원유 제품을 분리 후 회전 증발 용의 빛 노란색 기름 제품 월급 eluent로 에틸 아세테이트/석유 에테르. 1:4 에틸 아세테이트/석유 에테르를 사용 하 여 개발 TLC 판, Rf = 0.4. 더 아래 분쇄 단계를 사용 하 여 유성 제품을 정화.</li>
	<li>Methanolto 유성 제품의 5 mL을 추가 하 고 위해 2 분 수집 결과 오프 화이트 솔리드 sonicate 흡입 여과 사용 하 여 (항복: 59%).</li>
</ol>3. HTT Pb 프레임 워크 자료의 단일 결정의 준비
<ol><li>PbOAc·3H2O 11.4 mg을 혼합 (0.030 mmol)의 명확한 솔루션으로 만들기 위해 유리병에 에틸렌 diamine 1.0 ml.</li>
	<li>HVaTT의 9.1 mg 로드 (0.010 mmol), NaOH의 사전 degassed 메탄올 솔루션의 2.0 mL (70 mmol/L), 그리고 빈 10 mL 유리병으로 에틸렌 diamine 1.0 mL와 5 분 동안 sonicate.</li>
	<li>PbOAc 솔루션 sonicated HVaTT 혼합물을 추가 합니다. 1 분, N2 와 반응 혼합물을 거품 그리고 유리병을 밀봉 하 나사 모자에 넣어.</li>
	<li>자연 냉각 실내 온도에 노란색-오렌지 동안 팔 면 단일 결정 적합 한 단일 결정 x 선 회절 연구 형성 되었다 대 한 뒤 48 h에 대 한 오븐에서 90 ° C에 유리병 열 (항복: 45%).</li>
	<li>결정에서 여과 흡입 하 고 신속 하 게 MeOH와 씻어. 실내 온도에 저장에 대 한 답답한 MeOH (5 mL)을 포함 하는 유리병에 크리스탈 유리 dropper를 전송 합니다.</li>
</ol>4. HTT Pb 크리스탈 파라콰트 Diiodide의 상호 작용
<ol><li>사용 하 여 유리 파스퇴르 피펫으로 MeOH 주식에서 HTT Pb 단 결정의 몇 가지 곡물을 철회 하 고 페 트리 접시에에 놓습니다 (직경 35 mm와 깊이 10 m m). 조직 또는 필터 종이 메탄올 액체를 흡수 (또는 MeOH 자연스럽 게 건조 하 게), 다음 몇 방울 파라콰트 diiodide (0.1%, w/w)의 수성 해결책의 결정에 놓습니다.</li>
	<li>색상을 관찰 눈 또는 현미경 결정의 변화.</li>
</ol>

<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. (10), 749-759 (1988).</li><li>Tiecco, M., Tingoli, M., Testaferri, L., Chianelli, D., Maiolo, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+dealkylation+of+bis[alkylthio]benzenes:+elimination-substitution+competition+with+methoxide+and+methanethiolate+ions+in+hexamethylphosphoric+triamide.">Selective dealkylation of bis[alkylthio]benzenes: elimination-substitution competition with methoxide and methanethiolate ions in hexamethylphosphoric triamide.</a> Synthesis. (6), 478-480 (1982).</li><li>Wark, T. A., Stephan, D. 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저자는 공개 없다.

브 그룹 및 thiomethoxide 음이온 사이의 반응은 분명히 먼저 다음 초과 thiomethoxide thiolate 음이온 제품을 제공 하 여 demethylated는 메 틸 thioether 생산. (특히에 대 한 HBT 같은 polybromide 기판) 원하는 thiolate 음이온을 완전 한 변환 되도록의 활발 한 조건 (예를 들어, 3을 통해 나트륨 thiomethoxide의 큰 과잉을 가진 난방 (예를 들어, 240 ° C 이상 48 h) 연장 배 브 그룹의 두더지) 필수적입니다. 질소 보...

강한, polarizable 금속-황 고용에 현재 큰 관심 있다 (예., 금속 thiolate) 건설에 대 한 링크 오픈 프레임 워크 자료 향상 된 electrocatalytic와 전도성 속성1,2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10. 홍보 전자 상호 작용 및 확장 된 상태에서 전송, 뿐만 아니라 부드럽고 화학식 금속 황 링크 또한 수성 환경에서 응용 프로그램에 대 한 더 나은 안정성을 얻으며. 황 장착 빌딩 블록, 대칭, 중 multidentate 다 환 방향족 빌딩 블록 처럼 2,3,6,7,10,11 triphenylene hexathiol (HTT)9,11,,1213 , 14 높은 polarizable π-전자, 공급 뿐만 아니라 프레임 워크 설계 및 합성에 관하여 뚜렷한 장점을 제공. 첫째, 엄격한 대칭 triphenylene 코어, HTT, chelating dithiolene 그룹과 함께에서 제공 일반 결합 모티프, 예비 네트워크7, 의 구조 예측을 단순화에 금속 이온에 고정 15. 황 링커의 엄밀 하 고 오픈 형상을 함께 실질적인 다공성 기능을 갖춘 프레임 워크 구조 자주 달성 될 수 있다 고체 상태에서.
Thiol 장착 금속 orangic 프레임 워크 (MOF) 재료의 조립에 하나의 주요 도전 유기 링커 분자 합성에 뿌리입니다. 클래식 프로토콜에서 thiol 그룹 O-aryl thiocarbamate 전조16,,1718의 뉴 먼 Kwart 재배치를 사용 하 여 페 놀 그룹에서 파생 했다. 그러나이 방법은,, 페 놀 선구자 분자 뿐만 아니라 높은 온도 단단한 단계 변화의 잠재적인 합병증에 대 한 정교한 대리점 단계를 포함 한다. Thiols를 만드는 또 다른 방법은 thioethers의, 예를 들어 나트륨 금속 액체 암모니아19,20,,2122, 가혹한 조건에서의 감소 dealkylation를 활용 하 고 되지 않습니다. carboxyl와 네트워크 건설에 대 한 다른 많은 기부자 기능 호환.
비교 하 여, 여기에 제시 된 프로토콜은 여러 장점: 안전, 편의 비용 효율성, 그리고 호환성 다른 기능 그룹을 (예., carbonitrile 및 pyridinyl). 적극적으로 일반적으로 저렴 한 향기로운 할로겐을가 열 하 여 (예., hexabromotriphenylene)과 thiomethoxide 음이온, thiolate 음이온 (메 틸 thioether 중간 제품)을 통해 생성 된 및 다음 acylated을 주고 안정 및 한 냄비에 쉬운 손잡이 thioester 제품-모든
우리는 또한 단일 결정 반도체 및 다공성 금속 dithiolene 네트워크에 액세스 하기 위한 thiol 링커의 마스크 형태로 thioester 분자를 이용 하는 절차를 설명 합니다. 분해 하 고 금속 thiolate 오픈 프레임 워크의 결정 화를 복잡 하 게 하는 경향이, 반응성이 매우 높은 무료 서 thiols 달리는 thioester 수 수 쉽게 죽 습 (예., NaOH 또는 ethylenediamine) 현장에 제공 하는 thiol 종, mercaptan 단위 및 금속 센터 사이 반응을 완화 하 고 결과적으로 결정 화를 개선 하기 위해 봉사.
이 프로토콜의 thiol/thioester를 준비 하 고 사용 되지 않은 널리 다른 그룹에 의해 금속 황 프레임 워크의 신흥 분야에 대 한 및 dealkylations thiolate 음이온에 의해 알 킬 aryl thioethers의 유기에 의해 이미 잘 문서화 되어 있지만 화학자23,,2425,26. Thioesters이 효율적인 합성 방법 및 금속-황 네트워크의 결정 화 촉진을 위한 그들의 사용을 보여주는, 우리가 지적 하 고 실용적인 합성 유기 화학 사이 분할을 다리를 더욱 노력을 촉진 하고자 하 고 고체 화학, 다공성 프레임 워크의 신속 하 고 건강 한 발달을 돕기 위해.

<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

선물이 thiol 링커 및 매우 정렬 된 단일 결정 상태에서 반도체 및 다공성 금속 dithiolene 네트워크에 액세스 하기 위한 그들의 사용의 마스크 형태로 thioester 분자를 준비 하는 방법. 분해 및 금속 thiolate 오픈 프레임 워크의 결정 화를 복잡 하 게 하는 경향이, 반응성이 매우 높은 무료 서 thiols 달리는 thioester 반응 제자리에 thiol 종, 사이 반응을 완화 하기 위해 봉사를 제공 하는 mercaptan 단위 및 금속 센터, 따라서 결정 화를 개선 하기 위해. 특히,는 thioester 한 냄비 절차에서 합성 되었다: 방향족 브롬 (hexabromotriphenylene) 먼저 thioether 중간 제품을 형성 하기 위하여 격렬 한 조건 하에서 과잉 나트륨 thiomethoxide와 함께 반응. thioether 다음 초과 thiomethoxide acylated thioester 제품을 형성 하는 thiolate 음이온을 제공 하 여 demethylated 했다. thioester 편리 하 게 표준 열 크로마토그래피에 의해 순화 되었다 고 다음에 직접 사용 프레임 워크 합성, NaOH와 ethylenediamine 현장에 복귀 하기 위하여 봉사 하는 점에서 thiol 링커에 thioester 조립은 단일-결정 Pb (II)-dithiolene 네트워크. Thiol 합성에 대 한 다른 방법에 비해 (예., 알 킬 thioether 나트륨을 사용 하 여 고착 하 여 금속 및 액체 암모니아), thioester 합성 여기 간단한 조건 및 경제적인 시 약을 사용 하 여. 또한, thioester 제품 안정 되어 수 편리 하 게 처리 하 고 저장. 더 중요 한 것은, 결정 금속-thiolate 오픈 프레임 워크 액세스 일반 어려움, 달리 설명 그는 thioester를 사용 하 여 제자리에 thiol 링커의 형성은 크게 향상는 고체의 결정 제품입니다. 우리는 thioester 뿐 아니라 고체 결정 프레임 워크에 대 한 합성 프로토콜을 공개 하 여 기술적으로 중요 한 금속-황 프레임 워크에 광범위 한 연구 활동을 장려 하고자 합니다.

(KBr 펠 릿 메서드에서 수집) HVaTT 분자의 IR 스펙트럼 1700 c m-1thioester 기능 그룹의 카보닐기 스트레칭 따라에서 그것의 강한 흡수를 갖추고 있습니다. HVaTT (400 MHz, CDCl3)의 1H NMR 스펙트럼 내의 지방 족 양성자에서 4 multiplets 함께 향기로운 hydrogens에서 δ 8.47에서 보여준다: δ 8.47 (s, 6 H, CHAr), 2.75-2.72 (t, J = 7.4, 12 H, 채널2), 1.81-1.77 (m, 12 H, 채?...

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

여기, 우리 thiols의 한 냄비, 전환-금속-무료 합성을 제시 하 고 향기로운 할로겐, 나트륨 thiomethoxide, 뒤에 thiol 종을 사용 하 여 금속 dithiolene 네트워크의 단일 결정의 준비에서 thioesters 생성 에서 해 라 더 안정적이 고 그러므로 thioester에서.

반도체 Gyroidal 금속-황 프레임 워크의 결정 화에 대 한 Thiol 빌딩 블록의 합성

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

synthesis-thiol-building-block-for-crystallization-semiconducting

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8.9K 조회수.  Guangdong University of Technology. 여기, 우리 thiols의 한 냄비, 전환-금속-무료 합성을 제시 하 고 향기로운 할로겐, 나트륨 thiomethoxide, 뒤에 thiol 종을 사용 하 여 금속 dithiolene 네트워크의 단일 결정의 준비에서 thioesters 생성 에서 해 라 더 안정적이 고 그러므로 thioester에서.

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

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the 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 molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

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

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

준비와 사마륨 Diiodide 이용 (SMI<sub&gt; 2</sub&gt;) 유기 합성의 : 사마륨 Barbier 반응에 HMPA과 니켈 (II) 소금의 기계론의 역할

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

연구

화학

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

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 &#176;C in the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 &#176;C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control.
Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to activity IV, as a suitable stationary phase has allowed isolation of certain iodoaziridines in excellent yield and purity.

A protocol for the diastereoselective one-pot preparation of cis-N-Ts-iodoaziridines is described. The generation of diiodomethyllithium, addition to N-Ts aldimines and cyclization of the amino gem-diiodide intermediate to iodoaziridines is demonstrated. Also included is a protocol to rapidly and quantitatively assess the most appropriate stationary phase for purification by chromatography.

합성 및 크로마토 그래피에 대한 최적의 고정상의 양이 선택의 참여 Iodoaziridines의 정화

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

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2&#183;H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior.

A two dimensional model material of discotic zirconium phosphate was developed. The inorganic crystal with lamellar structure was synthesized by hydrothermal, reflux, and microwave-assisted methods. On exfoliation with organic molecules, layered crystals can be converted to monolayers, and nematic liquid crystal phase was formed at sufficient concentration of monolayers.

합성 및 디스코 틱 지르코늄 인산염의 각질 제거는 콜로이드 액체 크리스탈을 구하는

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

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline elastomers (LCEs) with facile control over network structure and programming of an aligned monodomain. Tailored LCE networks were synthesized using routine mixing of commercially available starting materials and pouring monomer solutions into molds to cure. An initial polydomain LCE network is formed via a self-limiting thiol-acrylate Michael-addition reaction. Strain-to-failure and glass transition behavior were investigated as a function of crosslinking monomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). An example non-stoichiometric system of 15 mol% PETMP thiol groups and an excess of 15 mol% acrylate groups was used to demonstrate the robust nature of the material. The LCE formed an aligned and transparent monodomain when stretched, with a maximum failure strain over 600%. Stretched LCE samples were able to demonstrate both stress-driven thermal actuation when held under a constant bias stress or the shape-memory effect when stretched and unloaded. A permanently programmed monodomain was achieved via a second-stage photopolymerization reaction of the excess acrylate groups when the sample was in the stretched state. LCE samples were photo-cured and programmed at 100%, 200%, 300%, and 400% strain, with all samples demonstrating over 90% shape fixity when unloaded. The magnitude of total stress-free actuation increased from 35% to 115% with increased programming strain. Overall, the two-stage TAMAP methodology is presented as a powerful tool to prepare main-chain LCE systems and explore structure-property-performance relationships in these fascinating stimuli-sensitive materials.

A novel methodology is presented to synthesize and program main-chain liquid-crystalline elastomers using commercially available starting monomers. A wide range of thermomechanical properties was tailored by adjusting the amount of crosslinker, while the actuation performance was dependent on the amount of applied strain during programming.

이단 티올 레이트 반응을 이용하여 프로그래밍 주쇄 액정 엘라스토머의 합성

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

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

바이오 메디컬 응용 프로그램에 적합 InP를 /의 ZnS 양자점 CD-자유의 합성

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

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

HKUST 바닐린-1의 합성에 대해 불균일 촉매로서

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

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and &#946; liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

A protocol for in situ aqueous synthesis of a bis(iminoguanidinium) ligand and its utilization in selective separation of sulfate is presented.

비스 - iminoguanidinium의 리간드 선택적 결정화에 의한 황산염 분리

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

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

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

Ultrathin 높은 성능 금속-유기 프레임 워크 막의 전기 이동 화

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

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 solid-phase synthesis, regenerating Michael (REM) linker strategies, and 1,3-dipolar cycloaddition, a library of structurally similar heterocycles, both with and without a spirocyclic center, can be constructed. The main advantages of the solid-support synthesis are as follows: first, each reaction step can be driven to completion using a large excess of reagents resulting in high yields; next, the use of commercially available starting materials and reagents keep the costs low; finally, the reaction steps are easy to purify via simple filtration. The REM linker strategy is attractive because of its recyclability and traceless nature. Once a reaction scheme is completed, the linker can be reused multiple times. In a typical solid-phase synthesis, the product contains either a part of or the whole linker, which can prove undesirable. The REM linker is &#34;traceless&#34; and the point of attachment between the product and the polymer is indistinguishable. The high diastereoselectivity of the intramolecular 1,3-dipolar cycloaddition is well documented. Limited by the insolubility of the solid support, the reaction progression can only be monitored by a change in the functional groups (if any) via infrared (IR) spectroscopy. Thus, the structural identification of intermediates cannot be characterized by conventional nuclear magnetic resonance (NMR) spectroscopy. Other limitations to this method stem from the compatibilities of the polymer/linker to the desired chemical reaction scheme. Herein we report a protocol that allows for the convenient production of spirocyclic heterocycles that, with simple modifications, can be automated with high-throughput techniques.

Here we present a protocol to demonstrate an efficient method for the synthesis of spirocyclic heterocycles. The five-step process utilizes solid-phase synthesis and regenerating Michael linker strategies. Generally difficult to synthesize, we present a customizable method for the synthesis of spirocyclic molecules otherwise inaccessible to other modern approaches.

[4.4] Spirocyclic Oximes의 고체 상 합성

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 ...