Name: 1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions
Uploaded: 2016-10-10T13:00:00.000+00:00
Duration: 6 min 56 s
Description: Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

저자는이 프로젝트를 위해 교육 2 단계 연구 기금의 싱가포르 교육부 (프로젝트 MOE2013-T2-2-002)에서 자금을 인정합니다.

1,3,5- 트리 페닐 1. 준비 절차 (1) <ol><li> 자기 교반기, 환류 응축기, 질소 유입구, 버블, 적하 깔대기 및 온도계를 구비 한 둥근 바닥 삼구 250 mL의 플라스크에 아세토 페 논의 혼합물 (4.0 g, 33.3 mmol) 및 무수 에탄올 100 mL로 놓는다. 적하 깔때기를 사용하여 질소하에 0 ℃에서 한번에 혼합물에 사염화 규소 (11.9 g, 8.0 ㎖, 70.2 밀리몰, 2.1 당량). 추가. </li><li> 10 분 기상 염화수소의 진화를 관찰한다. 이어서 20 시간 동안 40 ℃에서 반응 혼합물을 교반 하였다. </li><li> 23 ° C의 반응 혼합물을 냉각시키고 얼음과 혼합하여 물 200 g 중에 부어 (1 : 1 중량비). </li><li> 추출 깔때기를 사용하여 디클로로 메탄 (2 × 100 mL)로 생성 된 혼합물을 추출 하였다. </li><li> 포화 염화나트륨 수용액 (100 ㎖), 무수 MgSO4로 건조하여 15 g 번 합한 추출물을 세척한다. 오프 액체 부분을 필터링 한 다음 우리를 집중회전 증발기를 보내고. </li><li> 2.2 g (63 % 수율) 1,3,5- 트리 페닐 벤젠의 에탄올을 얻기 재결정을 통해 생성물을 정제 (밤새 6 ℃로 유지하는 용매의 부분 증발시켜 에탄올을 최소량에 용해하고, 신속한 여과) (1)을 담황색 결정으로서 얻었다. 주 : 1 H-NMR (400 MHz의, CDCl3 중). δ = 7.41 (m, 3H), 7.50 (m, 6H), 7.72 (d, 6H, J = 7.33Hz), 7.80 (S, 3H) 13 C-NMR (400 MHz의, CDCl3 중) = 125.21, 127.39, 127.57, 128.88, 141.18, 142.38 δ. </li></ol> 2. LiSES는 1,3,5- 트리 페닐와 준비 <ol><li> 1,3,5- 트리 페닐 기반 LiSES의 제조 참고 :이 문서에 사용 된 1,3,5- 트리 페닐는 위에서 설명한 절차에 따라 합성 하였다. 리 붙이고 1,3,5- 트리 페닐 기반 LiSES X는 리튬 나타내고 TPB (THF) 24.7 X : PAH 몰비 및 TPB는 1,3,5- 트리 페닐이다. 리 준비X TPB (THF) 다음의 단계를 통해 상온에서 아르곤 충진 글로브 박스 내부 24.7 : <ol><li> 리튬의 타겟 몰 조성물 TPB (THF), X = 1, 2, 3 및 4를 사용하여 41.6 ㎎, 83.3 ㎎을 24.7, 124.9를 X 달성 별도로 글로브 박스 내부에 금속 리튬, THF 및 TPB의 잘 정의 된 양을 측정하여 ㎎, 각각, X = 1, 2, 3 및 4의 리튬 166.6 mg을. </li><li> 네 LiSES 샘플을 각각 제조 할 경우, 각 병 TPB (THF) 24.7 무색 용액 12 ml를 형성하는 네 개의 분리 된 유리 병 안에 THF 12 ㎖에 TPB 1.84 g을 용해. 모든 솔루션에 0.5 M 1,3,5- 트리 페닐를 사용합니다. </li><li> 네 병에 리 포일 현탁 금속을 추가하고 파라 필름으로 병을 밀봉. </li><li> 금속 리튬의 완전한 용해를 보장하기 위해 유리 코팅 된 자석 교반기를 사용하여 각 병의 혼합물을 밤새 교반한다. </li></ol></li><li> 전도도 측정 <ol><li> 나르다네 개의 전극 기술에 기반한 표준 전도도 셀 프로브를 사용하여 모든 전도도 측정. 미터에 셀 프로브를 연결합니다. 프로브는 동시에 액의 온도를 측정하고, 두 전도성 및 온도 측정을 표시하기위한 보조 기능을 갖는다. </li><li> 이전 측정을, 글로브 박스 밖에서 도전 프로브의 제조에 의해 제공되는 표준의 KCl 수용액 0.01 M 용액 50 ㎖를 이용하여 미터를 보정. </li><li> 1,3,5- 트리 페닐 계 LiSES 모든 전도성 측정을 수행, 리 TPB (THF) 글로브 박스 내부 X = 1, 2, 3, 4 24.7 X. </li><li> 이러한 LiSES마다 짧은 유리 실린더에 시료를 부어 용액에 프로브를 담궈. 주위 온도로 복귀까지 각 샘플 1 ~ 2 시간에 걸쳐 도전율 측정을 기록한다. 주위 온도로 복귀하도록 각 샘플에 대해 걸리는 시간 ~ 1-2 시간이다. 프로브 w병 전도도 측정 전체 기간의 샘플에 침지 유지. </li></ol></li></ol> 3. Corannulene <ol><li> corannulene 기반 LiSES의 제조 참고 :. PAH 몰 : 본 연구에 사용 된 corannulene는 다단계 문학 절차를 사용하여 물리 학부 및 수학 과학, NTU에서 합성 9 corannulene 기반 LiSES는 리튬로 표시된다 x는 리튬을 나타낸다 고전 (THF) 247 X 비와 고전은 corannulene이다. 준비 리튬은 다음과 같은 단계를 통해 상온에서 아르곤 충진 글로브 박스 (247) 내부에 고전 (THF)를 X : <ol><li> 리 고전 X 이용 4.2 ㎎, 8.3 mg의 X = 1, 2, 3, 4 및 5에 대한 247 (THF)을 대상 몰 조성을 달성하도록 개별적으로 글로브 박스 내부에 금속 리튬, THF 및 고전의 잘 정의 된 양을 측정하여 12.5 ㎎, 16.6 ㎎을 각각 X = 1, 2, 3, 4 및 5에 대한 리튬의 20.8 밀리그램. </li><li> 넥스t, 다섯 LiSES 샘플 (X = 1, 2, 3, 4, 5)는, 5 개의 개별 유리 병 안에 THF 12 ㎖에 고전 0.15 g을 용해 제조되는 각각 고전 무색 용액을 12 ml의 형성 각 병 (THF) 247. ) 0.05 M의 corannulene 농도를 사용합니다. </li><li> 다음으로, 리는 고전 (THF) 247의 다섯 병에 포일 현탁 금속을 추가하고 파라 필름으로 병을 밀봉. </li><li> 금속 리튬의 완전한 용해를 보장하기 위해 유리 코팅 된 자석 교반기를 사용하여 각 병의 혼합물을 밤새 교반한다. </li></ol></li><li> 전도도 측정 <ol><li> 온도 측정 대 도통, 리 고후 (THF), X = 1, 2, 3, 4, 개별적 글로브 박스에서 5 247 X 함유 다섯 병의 각각을 제거 파라 필름의 추가 층을 감고 젖어 드라이 아이스로 채워진 절연 스티로폼 용기 내부. 참고 : LiSES 샘플을 계속에 오지 않았다병 밀봉 되었기 때문에 글러브 박스 외부 동안 수분이나 산소 중 행동. </li><li> 전도도 측정을위한 글로브 박스로 다시 전송되기 전에 약 30 분 동안 드라이 아이스에 침지 각각의 병을 유지하여 약 10 ° C에 이르기까지 각 병 쿨. </li><li> 각각 5 회 이상이 축합 물 흔적 다시 글로브 박스로 병을 동반하지 않도록 샘플을 냉각시키고 글로브 박스의 앤티 챔버 퍼지. </li><li> 온도 측정 대 도전성 나프탈렌 계 LiSES 샘플 1을 수집하는 방식, 리튬의 전도도를 측정 마찬가지로 247 (X = 1, 2, 3, 4, 5)는 하나의 기간에 고전 (THF)을 X 각 샘플까지 두 시간 실온으로 돌아왔다. 프로브는 전도도 측정 전체 기간 동안 시료 중에 침지 상태로 유지된다. </li></ol></li></ol>

<ol>
	<li>Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Physical-Chemical+and+Electrochemical+Studies+of+the+Lithium+Naphthalenide+Anolyte.">Physical-Chemical and Electrochemical Studies of the Lithium Naphthalenide Anolyte.</a> Electrochim Acta. 180, 629-635 (2015).</li><li>Tan, K. S., Grimsdale, A. C., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Characterisation+of+Biphenyl-Based+Lithium+Solvated+Electrons+Solutions.">Synthesis and Characterisation of Biphenyl-Based Lithium Solvated Electrons Solutions.</a> J Phys Chem B. 116, 9056-9060 (2012).</li><li>Rinaldi, A., Tan, K. S., Wijaya, O., Wang, Y., Yazami, R., Menictas, C., Skyllas-Kazacos, M., Lim, T. M., Hughes, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ch.+11.">Ch. 11.</a> Advances in batteries for large- and medium-scale energy storage applications in power systems and electric vehicles. , (2014).</li><li>Wang, Y., Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Materials Challenges In Alternative &amp; Renewable Energy (MCARE 2014). , (2014).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> in 8th annual Li Battery Power. , (2012).</li><li>Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hybrid+Electrochemical+Generator+With+A+Soluble+Anode.">Hybrid Electrochemical Generator With A Soluble Anode.</a> US patent. , (2010).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Liquid+Metal+Battery.">Liquid Metal Battery.</a> US patent. , (2015).</li><li>Lim, Z. B., 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=Synthesis+and+assessment+of+new+cyclopenta-2,4-dienone+derivatives+for+energy+storage+applications.">Synthesis and assessment of new cyclopenta-2,4-dienone derivatives for energy storage applications.</a> Synthetic Met. 200, 85-90 (2015).</li><li>Butterfield, A. M., Gilomen, B., Siegel, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kilogram-Scale+Production+of+Corannulene.">Kilogram-Scale Production of Corannulene.</a> Org. Process Res. Dev. 16, 664-676 (2012).</li><li>Elmorsy, S. S., Pelter, A., Smith, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+direct+production+of+tri-+and+hexa-substituted+benzenes+from+ketones+under+mild+conditions.">The direct production of tri- and hexa-substituted benzenes from ketones under mild conditions.</a> Tetrahedron Lett. 32, 4175-4176 (1991).</li><li>Zabula, A. V., Filatov, A. S., Spisak, S. N., Rogachev, A. Y., Petrukhina, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Main+Group+Metal+Sandwich:+Five+Lithium+Cations+Jammed+Between+Two+Corannulene+Tetraanion+Decks.">A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks.</a> Science. 333, 1008-1011 (2011).</li></ol>

저자는 공개 아무것도 없어.

1,3,5- 트리 페닐 계 LiSES 들어, 광 컬러 샘플은 용 매화 전자의 낮은 농도를 갖는 것을 보여준다. 리 TPB (THF) 24.7 (X = 1, 2, 3, 4) 비 페닐 나프탈렌 1에서 만든 LiSES위한 본 유사한 X 대 전도성의 동작을 보여 2 .There 도전성의 초기 증가는 X 1~2 PAH 비율과 상기 리튬 1 TPB (THF) 247보다 훨씬 더 낮은 리튬 4 TPB (THF) 24.7 전도도 값, 3 및 4의 ?...

리튬 매화 전자 솔루션 (LiSES)는 이러한 비 페닐 및 나프탈렌과 같은 간단한 2 링 폴리 방향족 탄화수소 (PAH)가 잠재적으로 refuelable 리튬 전지 1-7 액체 양극으로 활용 될 수 사용하여 제조. LiSES, 이러한 간단한 PAH 분자가 용해 된 금속 리튬의 매화 전자의 전자 수용체로 봉사했다. 이들 두 고리 계에서 진행 저자는 더 복잡한의 PAHs를 사용 펜타 -2,4- 사이 클릭 디에 논 유도체 (8)의 그룹으로부터 제조된다 LiSES에 도전 측정 연구를 수행 한 이후. 이들의 PAHs는 방향족 고리에 통합 치환기와 큰 PAHs의 (&gt; 두 개의 벤젠 고리)과 PAHs에 포함되어 있습니다. 두 개 이상의 고리와 큰 PAH 분자 따라서 높은 에너지 밀도와 LiSES 결과 페닐 또는 나프탈렌 하나 이상의 PAH 분자 당 리튬 원자를 수용 할 것으로 예상된다. 부터 소개의 목적의 PAHs에 치환기를 보내고은 PAH가 더 쉽게 전자를 수용하고 LiSES에서 다중 음이온으로 더 안정 될 수 있도록하는 것입니다. 높은 에너지 밀도 LiSES을 개발하기 위해 지속적인 노력의 일환으로,이 논문은 문헌 절차 (9)뿐만 아니라 1,3,5- 트리 페닐에 의해 corannulene에서 준비 LiSES의 특성에보고, TPB는 약간 수정 된 문헌 (10)에 의해 합성 . 도 1 (1)에 도시 된 바와 같이, 1,3,5- 트리 페닐이 두 개의 추가 페닐 고리의 3 위치와 동일한 환의 5 비 페닐 유도체로서 분류 될 수있다. 이 분자는 네 개의 벤젠 고리를 가지고 있기 때문에, 더 비 페닐에 대한보다 분자 당 리, 4 원자의 흡수해야하며, 나프탈렌 (0.5 M 용액 PAH 당 리튬의 최대 2.5 몰 당량) (&lt;분자 당 리튬 2.5 몰 당량) . Corannulene는도 1에 도시 된 바와 같이 PAH 그릇 형상으로 배치 된 오 - 링 (2,). Zabula 외. 11 corannulene 두 안정 tetraanions 끼워 다섯 리 + 이온과 용액을 형성 corannulene / 테트라 히드로 푸란 (THF)의 용액 중에서 금속 리튬을 용해 가능성을 보여 주었다. <img alt="그림 1" src="/files/ftp_upload/54366/54366fig1.jpg" /> 그림 1. 1,3,5- 트리 페닐이 같은 고리의 위치 3 및 5에 두 개의 추가 페닐 고리와 비 페닐 유도체로 분류 (1) corannulene (2) 1,3,5- 트리 페닐 벤젠의 분자 구조 . Corannulene 그릇 모양으로 배열 된 다섯 개의 벤젠 고리와 오 - 링 PAH입니다. <a href="https://www.jove.com/files/ftp_upload/54366/54366fig1large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭하십시오.</a> 따라서, 1,3,5- 트리 페닐 및 corannulene 모두 높은 에너지 후보는밀도 LiSES.

<table><tbody><tr><td>Tetrahydrofuran Anhydrous, &amp;#8805;99.9%, Inhibitor-free</td><td>Sigma Aldrich</td><td>401757-100ML</td><td></td></tr><tr><td>Lithium Foil&amp;nbsp;</td><td>Alfa Aesar</td><td>010769.14</td><td></td></tr><tr><td>Cond 3310 Conductivity Meter</td><td>WTW</td><td>Not Applicable</td><td></td></tr><tr><td>1,3,5-triphenylbenzene</td><td></td><td></td><td>Synthesized from acetophenone according to procedure described in literature</td></tr><tr><td>Silicon tetrachloride</td><td>Sigma Aldrich</td><td>215120-100G</td><td></td></tr><tr><td>acetophenone</td><td>TCI</td><td>A0061-500g</td><td></td></tr><tr><td>Ethanol</td><td>Merck Millipore</td><td>1.00983.2511</td><td></td></tr><tr><td>Corannulene</td><td></td><td></td><td>Synthesized by literature procedure</td></tr></tbody></table>

1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions

저자는 리튬 매화 전자 솔루션 (LiSES)에서 수행 전도도 연구에 대한 보고서를 전자 수용체로, 폴리 방향족 탄화수소의 두 가지 유형 (PAH), 즉 1,3,5- 트리 페닐 및 corannulene을 사용하여 제조. 고체의 PAHs 먼저 용액을 형성하기 위해 테트라 히드로 푸란 (THF)에 용해시켰다. 리튬 금속은 청색 또는 청녹색 솔루션 매화 전자의 존재를 나타내는 색상이다를 수득 이러한 PAH / THF 용액에 용해시켰다. 리 붙이고 1,3,5- 트리 페닐 계 LiSES상에서 수행 주위 온도에서 전도도 측정 TPB (THF)을 X 24.7 (X = 1, 2, 3, 4), 리튬의 증가 전도도의 증가를 나타내었다 : x는 1 내지 2로 PAH 비 그러나, 도전율이 서서히 상기 비율의 증가에 따라 감소 하였다. 실제로 리튬의 전도도는 TPB (THF) × = 4 24.7는 x의보다 낮은 X </em&gt; = 1 이러한 문제는 바이 나프탈렌으로부터 제조 이전에보고 LiSES 유사하다. 리 붙이고 corannulene 기반 LiSES에 온도 측정, 비교 전도도 고전 (THF) (247) (X = 1, 2, 3, 4, 5)에 나타내었다 페닐 유사한 금속성 거동을 나타내는 음의 기울기를 가진 직선 관계 및 나프탈렌을 X 기반 LiSES.

그림 2와 같이 다양한 리튬의 양 및 THF와 1,3,5- 트리 페닐의 혼합물의 반응은 녹색 청색 또는 깊고 푸른 색깔의 솔루션을 제공합니다. 빛 색상 LiSES의 특정 샘플 용 매화 전자의 낮은 농도가 있음을 나타냅니다. 0.5 M THF 용액 (표 1)에서 1 내지 2 PAH 비율 : 1,3,5- 트리 페닐 리튬의 증가 전도도 상승을 보여준다. 그러나, 전도성 값은 점차 상기 몰비의 증가에 따라 감소한다. 리튬...

Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

리튬 매화 전자 솔루션 전자 수용체로 1,3,5- 트리 페닐 및 Corannulene

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic ...

135-triphenylbenzene-corannulene-as-electron-receptors-for-lithium

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7.7K 조회수.  Nanyang Technological University. The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

비디오: 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

방사광 기술을 사용하여 리튬 이온과 나트륨 이온 배터리 용 전극 재료의 특성

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

연구

공학

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

이온 성 액체에 의해 매개 1,6- Ketoesters의 높은 입체 선택적 합성 : 저 분자량 젤 레이터의 새로운 클래스에 빠른 액세스를 가능하게하는 3 요소 반응

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

화학

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar polyaromatic units, which are two corannulene moieties and a racemic hexahelicene linking them. The compound described in this work is a good host for fullerenes. Several common organic reactions, such as free-radical reactions, C-C coupling or click chemistry, are employed demonstrating the versatility of functionalization that this compound can accept. All of these reactions work for planar aromatic molecules. With subtle modifications, it is possible to achieve similar results for nonplanar polyaromatic compounds.

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Here, we present a protocol to synthesize a complex organic compound comprised of three nonplanar polyaromatic units, assembled easily with reasonable yields.

구리 (I)에 의해 Corannulene 기능화 Hexahelicene의 제조 비평 아로마틱 유닛 알킨 지드의 고리 화를 촉매 반응

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar ...

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents warrants proper technique, thorough training, and proper personal protective equipment. To aid in the training of researchers using organolithium reagents, a thorough, step-by-step protocol for the safe and effective use of tert-butyllithium on an inert gas line or within a glovebox is described. As a model reaction, preparation of lithium tert-butyl amide by the reaction of tert-butyl amine with one equivalent of tert-butyl lithium is presented.

The safe and proper use of organolithium reagents is described.

유기 리튬 시약을 사용하여 안전 리튬 화의 반응을위한 프로토콜

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

보장<em&gt; N</em&gt; - 헤테로 사이 클릭 카벤 착물 : 벤즈 이미 다 졸리움 염으로부터의 합성 및 탄소 - 탄소 결합 형성 반응에서의 촉매 활성

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that derive from initial 2-bromo-2-butene lithiation followed by acid mediated dienol cyclization. The revised synthesis and purification of the ligand avoids the use of mechanical stirring while still permitting access to significant quantities (39 g) of Cp*H in good yield (58%). The procedure offers other additional benefits, including a more controlled quench of excess lithium during the production of the intermediate heptadienols and a simplified isolation of Cp*H of sufficient purity for metallation with transition metals. The ligand was subsequently used to synthesize [Cp*MCl2]2 complexes of both iridium and ruthenium to demonstrate the utility of the Cp*H prepared and purified by our method. The procedure outlined herein affords substantial quantities of a ubiquitous ancillary ligand support used in organometallic chemistry while minimizing the need for specialized laboratory equipment, thus providing a simpler and more accessible entry point into the chemistry of 1,2,3,4,5-pentamethylcyclopentadiene.

Reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented. The revised protocol for the synthesis and purification of the ligand minimizes the need for specialized laboratory equipment while simplifying reaction workups and product purification. Use of Cp*H in the synthesis of [Cp*MCl2]2 complexes (M = Ru, Ir) is also described.

가치있는 리간드에 액세스하면 전이 금속에 대한 지원 : 1,2,3,4,5-Pentamethylcyclopentadiene의 수정, 중간 규모 준비

A reliable, intermediate scale preparation of 1,2,3,4,5-pentamethylcyclopentadiene (Cp*H) is presented, based on modifications of existing protocols that ...

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

집중 된 이온 빔 제작 현장에서 테스트 LiPON 기반 고체 리튬-이온 Nanobatteries

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

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

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

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 ...

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Protocols for the isolation of the commonly employed cyclic (alkyl)(amino) carbene (CAAC) and N-heterocyclic carbene (NHC) are reported. Furthermore, the synthesis of their mixed CAAC&#8211;NHC &#8220;Wanzlick&#8221; dimer and the synthesis of the related stable organic &#8220;olefin&#8221; radical are presented. The main goal of this manuscript is to give a detailed and general protocol for the synthetic chemist of any skill level on how to prepare free heterocyclic carbenes by deprotonation using filter cannulas. Due to the air-sensitivity of the synthesized compounds, all experiments are performed under inert atmosphere using either Schlenk technique or a dinitrogen filled glovebox. Controlling Wanzlick&#8217;s equilibrium (i.e., the dimerization of free carbenes), is a crucial requirement for the application of free carbenes in coordination chemistry or organic synthesis. Thus, we elaborate on the specific electronic and steric requirements favoring the formation of dimers, heterodimers, or monomers. We will show how proton catalysis allows for the formation of dimers, and how the electronic structure of carbenes and their dimers affects the reactivity with either moisture or air. The structural identity of the reported compounds is discussed based on their NMR spectra.

We present protocols for the isolation of stable heterocyclic carbenes. The synthesis of a cyclic (alkyl)(amino) carbene (CAAC) and an N-heterocyclic carbene (NHC) is demonstrated using filter cannulas and Schlenk technique. We furthermore present the synthesis of the related oxygen-sensitive, electron-rich mixed &#8220;Wanzlick dimer&#8221; and the reduced stable organic radical.

무료 Carbenes, 그들의 혼합 이합체 및 유기 급진 파를 격리

Protocols for the isolation of the commonly employed cyclic (alkyl)(amino) carbene (CAAC) and N-heterocyclic carbene (NHC) are reported. Furthermore, the ...

Redox-Active MOF의 자기 측정 특성 분석 Solid-State Electrochemistry

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs show outstanding performance in terms of gravimetric or areal capacitance and cyclic stability, unfortunately their electrochemical mechanisms are not well understood in most cases. Traditional spectroscopic techniques, such as X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS), have only provided vague and qualitative information about valence changes of certain elements, and the mechanisms proposed based on such information are often highly disputable. In this article, we report a series of standardized methods, including the fabrication of solid-state electrochemical cells, electrochemistry measurements, the disassembly of cells, the collection of MOF electrochemical intermediates, and physical measurements of the intermediates under the protection of inert gases. By using these methods for quantitatively clarifying the electronic and spin state evolution within a single electrochemical step of redox-active MOFs, one can provide clear insight into the nature of electrochemical energy storage mechanisms not only for MOFs, but also for all other materials with strongly correlated electronic structures.

저자 스포트라이트: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks  

Ex situ magnetic surveys can directly provide bulk and local information on a magnetic electrode to reveal its charge storage mechanism step by step. Herein, electron spin resonance (ESR) and magnetic susceptibility are demonstrated to monitor the evaluation of paramagnetic species and their concentration in a redox-active metal-organic framework (MOF).

산화 환원 활성 금속-유기 프레임워크의 고체 전기화학에서 중간체의 자기 측정 특성 분석

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...