Name: scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-s,s-dioxide core
Uploaded: 2017-10-24T15:00:00.000+00:00
Duration: 8 min 51 s
Description: Watch this Scientific Journal Video about Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core at JoVE.com

이 연구는 H2020-MSCA-ITN-2015/674990 프로젝트 "EXCILIGHT" Marie Skłodowska 퀴리 부여 계약 유럽 연합의 지평선 2020 연구와 혁신 프로그램에서 자금을 받았다. 잠 옷 울프 연구 공로 수상 왕립 학회 감사.

주의: 사용 전에 모든 관련 물질 안전 데이터 시트 (MSDS)를 참조 하십시오. 합성에 사용 되는 화학 물질의 일부는 매우 독성과 발암 성 있습니다. 실리 카 젤을 작업할 때 입자 흡입을 방지 하기 위해 보호 호흡 마스크를 착용 해야 합니다. 화학 반응 공학 컨트롤 (증기 찬) 및 개인 보호 장비 (보호 안경, 장갑, 실험실 외 투, 전체 길이 바지, 폐쇄 발가락 신발)의 사용을 포함 하 여 수행할 때 모든 적절 한 안전 규칙을 준수 하십시오.
 모든 시 약 및 용 매 상업적으로 구입 했다 고 어떤 더 정화 없이 사용 되었다. 1 H 및 13 C NMR 스펙트럼 CDCl 3 용 매로 사용 하 여 400 MHz 핵자기공명 분석기에 기록 되었다. 양성자 NMR 화학 변화는 δ 값 deuterated 용 매를 기준으로 ppm으로 보고: CDCl 3 (7.26). 데이터는 다음과 같이 표시 됩니다: Hz.에 화학 변화, 다양성 및 constant(s) (J) 커플링 Multiplets 보고 (ppm)에 범위 그들은 나타났다. 탄소 NMR 데이터 해당 용 매 신호 CDCl 3 (77.16) 기준으로 수집 했다. 융 점 융 점 장치를 사용 하 여 측정 되었다. 매트릭스 보조 레이저 이온화-시간--비행의 (MALDI-TOF) 질량 분석 Shimadzu Axima-CFR 분석기에서 실행 했다 desorption (범위 1-150 000 다 대량).
 1. 보고 된 화합물의 합성 <ol><li>화합물 1 (3,6-di-tert-butyl-9H-carbazole)의 합성 19 <ol><li>500 mL 3 목을 사용 하 여 둥근 바닥 플라스 크, 디졸브 9- H-carbazole (10.0 g, 60 mmol) nitromethane (300 mL) 질소 대기권의 밑에. 그런 다음이 솔루션에 아연 (II) 염화 물 (24.3 g, 180 mmol)을 추가.</li>
		<li>100ml 추가 깔때기로 2-클로-2-methylpropane (19.5 mL, 180 mmol)을 부 어 하 고 활발 한 교 아래 dropwise 추가.</li>
		<li>6 헤에 대 한 실 온에서 결과 혼합물을 저 어</li>
		<li>모니터링 dichloromethane을 사용 하 여 얇은 층 크로마토그래피 (TLC)에 의해 반응의 완료: 헥 산 1:1 v/v eluent 혼합물으로. 9-H-carbazole의 소비 후 추가 솔루션을 무력화에 물 100 mL.</li>
		<li>때마다 세 번 dichloromethane의 150 mL와 함께 제품을 추출합니다. 수성 층에서 유기 레이어를 구분 하 고 또한 물 150 mL로 두 번 세척 합니다.
		<ol><li>황산 마그네슘의 15 g 결과 유기 레이어를 건조 하 고 회색 파우더를 감소 압력에서 용 매를 증발.</li>
		</ol></li> <li>칼럼 크로마토그래피 dichloromethane을 사용 하 여 찌 꺼 기를 정화: 헥 산 1:1 v/v는 eluent로 용 매 혼합물의 백색 분말으로 복합 1 13.1 g (79%)를 제공. 
		1 특성화 복합: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.12 (d, J = 1.9 Hz, 2 H), 7.78 (s b, 1 시간), 7.5 (dd, J = 8.5, 1.9 Hz, 2 H), 7.33 (dd, J = 5.6, 0.5 Hz, 2 H), 1.49 (s, 18h). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 142.4 138.2, 123.7, 123.4, 116.3, 110.2, 34.9, 32.2. 
		MS: m/z 279.4 (M +). 
		녹는점: 233-235 ° c.</li>
	</ol></li> <li>합성 화합물 2 (2, 8-dibromodibenzothiophene)의 20 <ol><li>클로 프롬 (100 mL) 질소의 밑에 dibenzothiophene (15.0 g, 81.3 mmol)을 녹 500 mL 3 목 둥근 바닥 플라스 크를 사용 하 여 분위기입니다. 다음, 활발 한 교 아래 0 ° C에 dropwise 브롬 (9.3 mL, 180 mmol)을 추가.</li>
		<li>브롬의 완전 한 추가 후 실내 온도에 온도 올리고 18 헤에 대 한 반응 혼합물을 저 어</li>
		<li>필터 결과 화이트에서 침전 하 고 반복적으로 세척 물 50 mL와 함께 다음의 백색 분말으로 23 g (83%)의 수익률에 2, 8-dibromodibenzothiophene을 메탄올 15 mL. 
		화합물 2 특성화: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.24 (d, J = 2.0 Hz, 2 H), 7.71 (d, J = 8.0 Hz, 2 H), 7.58 (d, J = 2.0 Hz, 2 H). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 138.8, 136.3, 130.5, 124.9, 124.3, 118.8. 
		MS: m/z 342.1 (M +). 
		녹는점: 227-229 ° C.</li>
	</ol></li> <li>합성 화합물 3 (2, 8-dibromodibenzothiophene-5-이산화)의 21 <ol><li>500 mL 둥근 바닥 플라스 크 2, 8-dibromodibenzothiophene (21.3 g, 60 mmol)의 서 스 펜 션 1-목 로드, 빙 초 산 (250 mL) 및 질소 분위기에서 2 시간에 대 한 환류에 과산화 수소 솔루션 (30 mL의 30% (w/w) H 2 O).</li>
		<li>실내 온도에 결과 혼합물을 냉각 하 고 백색 침전에서 필터링.</li>
		<li>하얀 가루의 물 15 mL 그리고 19.3 g (85%)를 메탄올 10 mL로 세 번 세척. 
		화합물 3 특성화: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.22 (d, J = 1.6 Hz, 2 H), 7.70 (d, J = 8.0 Hz, 2 H), 7.57 (d, J = 2 Hz, 2 H). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 133.3 130.4, 129.1, 125.6, 124.8, 124.3. 
		MS: m/z 374.1 (M +). 
		녹는점: 360-362 ° C.</li>
	</ol></li> <li>의 합성 컴파운드 4 (2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide) 22 <ol><li>분해 500 mL 3 목 둥근 바닥 플라스 크를 사용 하 여 2, 8- dibromodibenzothiophene-S, S-이산화 (0.45 g, 1.2 mmol)와 3,6-di-tert-butyl-9H-carbazole (0.80 g, 2.86 mmol) 무수 톨루엔 (250 mL)을 통해 활발 한 감동에서 15 분 동안 질소 버블링 하 여 드.</li>
		<li>가 후, 추가 tris(dibenzylideneacetone)dipalladium(0) (0.025 g, 0.03 m m o l)와 2-dicyclohexylphosphino-2 &#8242; 4, &#8242; 6, &#8242;-triisopropylbiphenyl (XPhos, 0.06 g, 0.12 mmol) 반응 혼합물에 또 다른 15 분 동안 해결책을 드 고. </li> <li>나트륨 tert-butoxide (0.32 g, 0.834 mmol) tert-butanol (6 mL)을 추가 하 고 15 분에 대 한 결과 혼합물을 드</li>
		<li>열 18 헤에 대 한 질소 분위기에서 110 ° C에서 반응 솔루션</li>
		<li>를 방 온도, 추가 물 (150 mL)와 dichloromethane (250 mL)으로 유기농 제품을 추출 물 150 mL로 두 번 유기 레이어를 씻어 진정.</li>
		<li>황산 마그네슘의 15 g 결과 유기 레이어를 건조 하 고 원유 제품을 얻기 위해 감소 된 압력에서 용 매를 제거.</li>
		<li>칼럼 크로마토그래피에 의해 원유 자료 정화 (eluent는으로 혼합 용 매를 사용 하 여: dichloromethane: 석유 에테르 1:1 v/v) 화합물 4 백색 고체 (0.58 g, 63%)으로 항복. 
		화합물 4 특성화: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 8.13 (d, J = 1.6 Hz, 4 H), 8.11 (d, J = 8.2 Hz, 2 H), 7.99 (d, J = 1.7 Hz, 2 H), 7.82 (dd, J = 8.2, 1.8 Hz, 2 H), 7.48 (dd, J = 8.7, 1.9 Hz, 4 H), 7.40 (d, J = 8.6 Hz, 4 H), (s, 36 H) 1.45. 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 144.4, 144.2, 138.5, 135.8, 133.4, 128.4, 124.4, 124.3, 119.5, 116.8, 109.2, 35.0, 32.2. 
		MS: m/z 769.97 (M +). 
		녹는점: 351-353 ° C.</li>
	</ol></li> <li>의 합성 화합물 5 (2,8-bis(10H-phenothiazin-10-yl)dibenzothiophene-S,S-dioxide) 23 <ol><li>Using 250 mL 3 목 둥근 바닥 플라스 크, 2, 8-dibromodibenzothiophene-S, S-이산화 (0.67 g, 1.8 m m o l) 및 phenothiazine (0.75 g, 3.77 mmol) 무수 톨루엔 (60 mL)에 녹이 고 활발 한 감동에서 15 분 동안 질소 통해 버블링 여 드.</li>
		<li>가 후, 추가 tris(dibenzylideneacetone)dipalladium(0) (0.11 g, 0.12 mmol)과 2-dicyclohexylphosphino-2 &#8242; 4, &#8242; 6, &#8242;-triisopropylbiphenyl (XPhos, 0.12 g, 0.23 m m o l) 반응 혼합물에 또 다른 15 분 동안 해결책을 드 고. </li> <li>나트륨 tert-butoxide (0.38 g, 3.94 mmol)을 추가 하 고 추가 15 분에 대 한 결과 혼합물을 드</li>
		<li>열 반응 솔루션 18 헤에 대 한 질소 분위기에서 110 ° c</li>
		<li>반응 혼합물 온도 룸, 물 (150 mL)을 추가 dichloromethane (250 mL)으로 유기농 제품을 추출 하 고 또한 물 150 mL로 두 번 씻어 내려 멋진.</li>
		<li>드라이 결과 유기 층은 황산 마그네슘 및 원유 제품을 주고 감소 된 압력에서 용 매 제거의 15 g.</li>
		<li>칼럼 크로마토그래피에 의해 원유 제품을 정화 (eluent는으로 용 매 혼합물을 사용 하 여: dichloromethane: 헥 산 2:1 v/v) 백색 고체 (0.9 g, 55%)로 화합물 5를. 
		화합물 5 특성화: 1 H NMR (400 MHz, CDCl 3, 25 ° C, ppm): 7.71 (d, J = 8.2 Hz, 2 H), 7.36 (dd, J 7.7, 1.5 Hz, 4 H =), 7.28-7.19 (m, 8 H), 7.16 (dd, J = 7.7, 1.3 Hz, 4 H), 7.02 (dd, J 8.1, 1.3 Hz = 4 H). 
		13 C NMR (400 MHz, CDCl 3, 25 ° C, ppm): 148.8 141.1, 133.2, 131.8, 129.7, 128.1, 126.9, 125.1, 125.3, 123.1, 121.2, 111.7. 
		MS: m/z 610.08 (M +). 
		녹는점: 353-355 ° C.</li>
	</ol>
	</li>
</ol>

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D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Studies+in+the+Sulfone+Series.+I.+The+Preparation+of+2,8-Diaminodibenzothiophene-5-dioxide.">Studies in the Sulfone Series. I. The Preparation of 2,8-Diaminodibenzothiophene-5-dioxide.</a> J. Am. Chem. Soc. 69, 1920-1921 (1947).</li><li>Gilman, H., Nobis, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rearrangement+with+4-Iododibenzothiophene+in+Amination+by+Sodamide.">Rearrangement with 4-Iododibenzothiophene in Amination by Sodamide.</a> J. Am. Chem. Soc. 67, 1479-1480 (1945).</li><li>Dias, F. 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=Triplet+Harvesting+with+100%+Efficiency+by+Way+of+Thermally+Activated+Delayed+Fluorescence+in+Charge+Transfer+OLED+Emitters.">Triplet Harvesting with 100% Efficiency by Way of Thermally Activated Delayed Fluorescence in Charge Transfer OLED Emitters.</a> Adv. Mater. 25, 3707-3714 (2013).</li><li>Dias, F. 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=The+role+of+local+triplet+excited+states+and+D-A+relative+orientation+in+thermally+activated+delayed+fluorescence:+photophysics+and+devices.">The role of local triplet excited states and D-A relative orientation in thermally activated delayed fluorescence: photophysics and devices.</a> Adv. Sci. 3, 1600080 (2016).</li><li>Moss, K. C., 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=Tuning+the+Intramolecular+Charge+Transfer+Emission+from+Deep+Blue+to+Green+in+Ambipolar+Systems+Based+on+Dibenzothiophene+S,S-Dioxide+by+Manipulation+of+Conjugation+and+Strength+of+the+Electron+Donor+Units.">Tuning the Intramolecular Charge Transfer Emission from Deep Blue to Green in Ambipolar Systems Based on Dibenzothiophene S,S-Dioxide by Manipulation of Conjugation and Strength of the Electron Donor Units.</a> J. Org. Chem. 75, 6771-6781 (2010).</li></ol>

공개 하는 것이 없다.

이 문서의 목적은 상용 원자재에서 OLED 응용 프로그램에 대 한 고효율 유기 물질 (그림 1)의 대규모 합성을 보여주는 것입니다. 우리가 그들의 전체 NMR 및 질량 분석 하는 모든 자료의 상세한 단계별 합성 보고만 이전 보고서 최종 크로스 커플링 반응 단계를 설명 하 고 오래 된 간행물의 일부를 참조, 그 사실 때문 특성 실험의 분석 향상된 재현성에 대 한
두 미터 곰 같은 이산화-dibenzothiophene-5 전자 수락자 코어. 복합 3 (그림 2)의 준비에 있는 첫걸음은 상용 dibenzothiophene 분자의 bromination 이다. 20 큰 규모 반응 하룻밤 83%의 수익률을 발생합니다. 결과 dibrominated 복합 2 빙 초 산, 여과 및 세척 후 하얀 가루의 19.3 g 저조한에 과산화 수소 솔루션 더 산화 될 수 있다. 21 복합 3 어떤 더 정화 없이 크로스 커플링 반응에 사용 되었다.
복합 4와 5 사이 photophysical 특성 차이 아민 단위의 전자 기증 속성에 놓여 있습니다. 화합물 중 하나는 주변 alkylated carbazole 단위 다른 phenothiazine 그룹 있다. Phenothiazine 분자 화학 공급 업체에서 구입 하 고 어떤 수정 없이 사용할 수 있습니다. 그러나, 복합 4 tert-부 틸 그룹의 경우 유기 용 매에 있는 가용성을 증가 하기 위하여 carbazole 단위의 향기로운 반지에 도입 해야 합니다. 적합 한 알 킬 그룹의 부재, 제품의 가용성 상품, 상당히 낮은 반응 수율 결과 보고 되었다. 24 알 킬 그룹 nitromethane electrophilic 아로마 대체 메커니즘에 따라 Friedel 기술 반응 tert-부 틸 염화 아연 (II) 염화 물 존재 9-H-carbazole 사이 사용 하 여 각 페 닐 링에 도입 될 수 있습니다. 19 그것은 발견 결과 제품의 순도 충분히 높지 않다 고 여러 부산물은 혼합물;에 따라서 원유 회색 분말 칼럼 크로마토그래피 결과 화합물 1 백색 분말으로 복구의 13.1 g의 분리에 의해 또한 정화 될 해야 합니다.
원하는 TADF 미터 4와 5는 문학 앞에서 설명한 절차를 사용 하 여 탄소-질소 팔라듐 촉매 크로스 커플링 반응을 통해 합성 했다. 22 , 23 우리는 부정 하지 않습니다 시작 자료의 금액을 증가 발견 반응 규모를 더 증가 가능한 제안 원하는 제품의 수익률에 영향. 4와 5 화합물 수 각각 63%와 55% 수율을 얻을.
결론적으로, 발광 전체 합성 절차 최대 규모 가능성과 함께 쉽게 사용할 수 있는 소재로 시작 하는 응용 프로그램에 대 한 고효율 유기 분자를 준비 하는 방법에 대 한 자세한 지침 입증 되었습니다. 이 작품을 통해 의도 다른 많은 TADF 미터의 대규모 합성 실험실 벤치에서 기술 산업 응용 프로그램의 빠른 전환을 보장 한다.

지난 몇 년간 연구원은 1987 년에 그들의 첫번째 소개부터 유기 분자와 유기 발광 다이오드 (Oled)에 그들의 파생 상품의 활용을 조사 있다. 1 기본 (엘)의 발견 유기 물질 디스플레이 조명에 다양 한 응용 프로그램을 찾는를 주도하 고 있다. 2 새로운 유기 화합물을 생산 하 고 그들의 photophysical 속성을 공부 거 대 한 관심; 기존 기술에 비해 Oled의 장점에 의해 구동 됩니다. 특히 그들은 더 에너지 효율적으로 높은 유연성, 작은 두께, 및 낮은 무게를 유지 하면서 우수한 장치 성능을 제공할 수 있습니다. 그럼에도 불구 하 고, 무기 발광 다이오드 (Led), 비해 Oled 대규모 상업 생산, 짧은 수명 낮은 효율성 등에서이 기술을 방지 하는 단점이 여전히 고통. 최근까지 대부분의 연구 1 세대 Oled 기반 그리고 방출 유기 물질의 형광에 의존. 사실은 형광 내의 상태 에서만에서 발생할 수 있습니다, 장치의 최대 이론적인 내부 양자 효율 (IQE)만 25%입니다. 3 , 4 , 5 (Ir, Pt) 등 중 금속 포함 유기농 단지를 이용 하 여 연구자는 복사 전환 과정에 의해 일 중 항 및 삼중 항 상태에서 전자를 수확 하 여 25% 효율 배리어를 극복할 수 있습니다. 6 , 7 , 8 따라서, 2 세대의 최대 이론적인 효율성 인광 Oled (PHOLEDs) 수 100%로 높은. 9 , 10 Nowadays, 많은 상업적인 OLED 장치 활용 녹색과 적색 인광 발광 유기 금속 복합물 이리듐에 기반 합니다. 11 이러한 자료는 모바일 디스플레이 및 기타 전자 애플리케이션에서 널리 사용을 얻고 있다, 하지만 중 금속 전조의 비용 소금 그리고 그들의 짧은 일생 대안 찾아 연구를 추진해 왔습니다.
OLED 기술, 높은 안정성, 효율적인 전력 소비와 소자의 낮은 생산 비용 등의 광범위 한 상용화에 대 한 달성 해야 하는 몇 가지 목표 있다. 최근 몇 년 동안, 그것은 열 활성화 지연된 형광 (TADF) 미터 지금 3 세대 OLED 물자로 간주 됩니다 이러한 자료와 동일한 IQE 값에 도달 PHOLED 재료에는 효과적인 대체할 수 표시 되었습니다. 12 , 13 , 14 순전히 유기 TADF 미터 전반적인 장치 제조 시장에 상업적으로 매력적인 만들기 쉽게 사용할 수 있는 시작 물자에서 몇 단계에서 준비 될 수 있습니다. 날짜 하려면, 거기는 몇 가지 포괄적인 문학 리뷰 장치 제작 소재 합성에서 모든 측면을 커버. 15,16,17,18 TADF 재료 준비와 주요 문제는 크로스 커플링 반응에 대 한 포함 하는 Pd 촉매를 사용 하 여. 위해 증가 규모 TADF 소재 준비에 대 한 가능성을 보여줍니다. 우리 조정-최대 자료 원하는 제품 4와 5 (그림 1)를 시작에서 TADF 미터의 합성. 22 , 23 이 상세한 프로토콜 TADF 재료의 합성와 관련 된 정보를 이해 하는 분야에서 새로운 실무자 수 있도록 위한 것입니다.

<table><tbody><tr><td>2-Chloro-2-methylpropane, 99+%</td><td>Sigma Aldrich</td><td>19780</td><td></td></tr><tr><td>2-Dicyclohexylphosphino-2&amp;prime;,4&amp;prime;,6&amp;prime;-triisopropylbiphenyl (XPhos), 97%</td><td>Sigma Aldrich</td><td>638064</td><td>Air sensitive</td></tr><tr><td>9-H-carbazole, 95%</td><td>Alfa Aesar</td><td>A11448</td><td>Air sensitive</td></tr><tr><td>Bromine, 99.5%</td><td>Fisher</td><td>10452553</td><td>Highly toxic</td></tr><tr><td>Chloroform, anhydrous, 99%</td><td>Sigma Aldrich</td><td>288306</td><td></td></tr><tr><td>Dibenzothiophene, 98%</td><td>Sigma Aldrich</td><td>D32202</td><td></td></tr><tr><td>Dichloromethane, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>270997</td><td></td></tr><tr><td>Glacial acetic acid, 99.7+%</td><td>Alfa Aesar</td><td>36289</td><td>Corrosive to skin</td></tr><tr><td>Hexane, anhydrous, 95%</td><td>Sigma Aldrich</td><td>296090</td><td></td></tr><tr><td>Hydrogen peroxide solution (30 % (w/w) in H&lt;sub&gt;2&lt;/sub&gt;O)</td><td>Sigma Aldrich</td><td>H1009</td><td>Corrosive to skin</td></tr><tr><td>Magnesium sulfate, 99.5%</td><td>Alfa Aesar</td><td>33337</td><td></td></tr><tr><td>Nitromethane, 98+%</td><td>Alfa Aesar</td><td>A11806</td><td>Highly explosive</td></tr><tr><td>Phenothiazine, 98+%</td><td>Alfa Aesar</td><td>A12517</td><td>Air sensitive</td></tr><tr><td>Sodium tert-butoxide, 97%</td><td>Sigma Aldrich</td><td>359270</td><td></td></tr><tr><td>Tert-butanol, anhydrous, 99.5%</td><td>Sigma Aldrich</td><td>471712</td><td></td></tr><tr><td>Toluene, anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>244511</td><td></td></tr><tr><td>Tris(dibenzylideneacetone) dipalladium(0), Pd 21.5% min</td><td>Alfa Aesar</td><td>12760-03</td><td>Air sensitive</td></tr><tr><td>Zinc (II) chloride, anhydrous, 98+%</td><td>Alfa Aesar</td><td>A16281</td><td></td></tr></tbody></table>

scale-up chemical synthesis of thermally-activated delayed fluorescence emitters based on the dibenzothiophene-s,s-dioxide core

우리 보고 선형 스케일-업 2, 8-bis (3,6-di-tert-butyl-9H-carbazol-9-yl) dibenzothiophene-S, S-이산화 (복합 4)과 2, 8-bis(10H-phenothiazin-10-yl) dibenzothiophene-S, 합성 하는 프로시저 S-이산화 (복합 5)를 사용 하 여 Buchwald Hartwig 크로스 커플링 반응 조건입니다. 또한, 우리 amination 크로스 커플링 반응에 필요한 모든 비 상업적으로 사용할 수 있는 시작 물자의 수직 합성을 보여 줍니다. 현재 문서에서 우리는 그들의 스펙트럼 특성 함께 설명된 화합물의 모든 합성 하는 자세한 절차를 제공합니다. 이 작품 광전자 응용 프로그램이 실제 장치에 그들의 구현을 용이 하 게 하는 큰 규모에 대 한 유기 분자를 생성 하는 가능성을 보여줍니다.

마지막 TADF 미터 (그림 1)의 화학 구조는 전자 기증 그룹 및 전자 철회 코어 레드 블루 표시 됩니다. Alkylated carbazole 파생과 dibrominated dibenzothiopene-S, S-이산화 수락자 분자 저렴 한 원자재 (그림 2)에서 준비 될 수 있습니다. 최종 제품 amination Pd 촉매 크로스 커플링 반응 (그림 3)의 대규모 버전으로 준비 될 수 있습니다.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56501/56501fig1.jpg"> 
그림 1 . 베어링의 3,6-di-tert-butyl-9H-carbazol-9-yl 및 10 H-phenothiazin-10-yl 기증자 moieties 2, 8-dibenzothiophene-5-이산화 전자 수락자 코어 (에 표시 된 빨간색)에 따라 열 활성화 지연된 형광 방출의 화학 구조 복합 4와 5를 각각 복합. 전자 기부 단체는 파란색으로 표시 됩니다. <a href="//ecsource-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56501/56501fig1large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56501/56501fig2.jpg"> 
그림 2 . 9-H-carbazole와 2, 8-dibromodibenzothiophene-5-이산화 (복합 3) 상용 dibenzothiophene에서 시작 하는 두 단계에의 알에 의해 준비 하는 3,6-di-tert-butyl-9H-carbazole (복합 1)으로 화학 반응 진학 <a href="//ecsource-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56501/56501fig2large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56501/56501fig3.jpg"> 
그림 3 . Buchwald-Hartwig 교차 하는 2, 8-dibromodibenzothiophene-5-이산화 (복합 3) 및 해당 보조 아민 간의 반응 결합 화합물 4와 5를 생산 하. <a href="//ecsource-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56501/56501fig3large.jpg" target="_blank">이 그림의 더 큰 버전을 보려면 여기를 클릭 하십시오.</a>

Watch this Scientific Journal Video about Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core at JoVE.com

Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

고효율 열 활성화 지연된 형광 방출의 스케일 업 합성 제시 문서에 설명 되어 있습니다.

스케일-업 Dibenzothiophene S, S-이산화 코어에 따라 열 활성화 지연된 형광 방출의 화학 합성

We report a procedure to linearly scale-up the synthesis of 2,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)dibenzothiophene-S,S-dioxide (compound 4) and ...

scale-up-chemical-synthesis-thermally-activated-delayed-fluorescence

Universidad San Sebastian

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JoVE Journal

Chemistry

9.5K 조회수.  University of Strathclyde. 고효율 열 활성화 지연된 형광 방출의 스케일 업 합성 제시 문서에 설명 되어 있습니다.

비디오: Scale-up Chemical Synthesis of Thermally-activated Delayed Fluorescence Emitters Based on the Dibenzothiophene-S,S-Dioxide Core

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to the preparation of new organic dyes. Although numerous strategies have been reported to access naphthalene scaffolds, many procedures still present limitations in terms of incorporating functionality, which in turn narrows the range of available substrates. The development of versatile methods for direct access to substituted naphthalenes is therefore highly desirable.
The Diels-Alder (DA) cycloaddition reaction is a powerful and attractive method for the formation of saturated and unsaturated ring systems from readily available starting materials. A new microwave-assisted intramolecular dehydrogenative DA reaction of styrenyl derivatives described herein generates a variety of functionalized cyclopenta[b]naphthalenes that could not be prepared using existing synthetic methods. When compared to conventional heating, microwave irradiation accelerates reaction rates, enhances yields, and limits the formation of undesired byproducts.
The utility of this protocol is further demonstrated by the conversion of a DA cycloadduct into a novel solvatochromic fluorescent dye via a Buchwald-Hartwig palladium-catalyzed cross-coupling reaction. Fluorescence spectroscopy, as an informative and sensitive analytical technique, plays a key role in research fields including environmental science, medicine, pharmacology, and cellular biology. Access to a variety of new organic fluorophores provided by the microwave-assisted dehydrogenative DA reaction allows for further advancement in these fields.

Microwave-assisted intramolecular dehydrogenative Diels-Alder (DA) reactions provide concise access to functionalized cyclopenta[b]naphthalene building blocks. The utility of this methodology is demonstrated by one-step conversion of the dehydrogenative DA cycloadducts into novel solvatochromic fluorescent dyes via Buchwald-Hartwig palladium-catalyzed cross-coupling reactions.

작용 Naphthalenes / Solvatochromic의 염료의 합성을위한 전자 레인지를 이용한 분자 Dehydrogenative Diels-앨더 반응

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to ...

연구

화학

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

전기 활성 고분자 나노 입자 출전 광열 등록

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

공학

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

단일 분자 수준에서 순환 고분자의 합성 및 용융 상태에서 그들의 확산 운동의 특성

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous networks, ribbons, worm-like aggregates, toroidal structures, and spherical particles) is described. These aggregates are morphologically influenced by extensive hydrophobic side chain-side chain interactions of the singular polycarbodiimide strands, as inferred by atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques. Polycarbodiimide-g-polystyrene copolymers (PS-PCDs) were prepared by a combination of synthetic methods, including coordination-insertion polymerization, copper(I)-catalyzed azide alkyne cycloaddition (CuAAC) &#34;click&#34; chemistry, and atom transfer radical polymerization (ATRP). PS-PCDs were found to form specific toroidal architectures at low concentrations in CHCl3. To determine the influence of a more polar solvent medium (i.e., THF and THF/EtOH) on polymer aggregation behavior, a number of representative PS-PCD composites have been tested to show discrete concentration-dependent spherical particles. These fundamental studies are of practical interest to the development of experimental procedures for desirable architectures by directed self-assembly in thin film. These architectures may be exploited as drug carriers, whereas other morphological findings represent certain interest in the area of novel functional materials.

Here, we present a protocol to prepare and visualize secondary structures (e.g., fibers, toroidal architectures, and nano-spheres) derived from helical polycarbodiimides. The morphology characterized by both atomic force microscopy (AFM) and scanning electron microscopy (SEM) was shown to depend on molecular structure, concentration, and the solvent of choice.

나선형 폴리 카 보디이 미드 공중 합체 및 이들의 트리아 졸 유도체로부터 획득 자기 조립 모폴로지

A facile method for the preparation of polycarbodiimide-based secondary structures (e.g., nano-rings, &#34;craters,&#34; fibers, looped fibers, fibrous ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables the acquisition of photoluminescence spectra covering the time regime from nanoseconds up to 0.1 s. This enables us to follow the changes in the intensity (decay) and emission of the spectra over time. Using this method, it is possible to study diverse photophysical phenomena, such as the emission of phosphorescence, and the contributions of prompt and delayed fluorescence in molecules showing thermally activated delayed fluorescence (TADF). Remarkably, all spectra and decays are obtained in a single experiment. This can be done for solids (thin film, powder, crystal) and liquid samples, where the only limitations are the spectral sensitivity of the camera and the excitation wavelength (532 nm, 355 nm, 337 nm, and 266 nm). This technique is, thus, very important when investigating the excited state dynamics in organic emitters for their application in organic light-emitting diodes and other areas where triplet harvesting is of paramount importance. Since triplet states are strongly quenched by oxygen, emitters with efficient TADF luminescence, or those showing room temperature phosphorescence (RTP), must be correctly prepared in order to remove any dissolved oxygen from solutions and films. Otherwise, no long-lived emission will be observed. The method of degassing solid samples as presented in this work is basic and simple, but the degassing of liquid samples creates additional difficulties and is particularly interesting. A method of minimizing solvent loss and changing the sample concentration, while still enabling to remove oxygen in a very efficient and a repeatable manner, is presented in this work.

Here, we present a method of the spectroscopic characterization of organic molecules by means of time-resolved photoluminescence spectroscopy on the nanosecond-to-millisecond timescale in oxygen-free conditions. Methods to efficiently remove oxygen from the samples and, thus, limit luminescence quenching are also described.

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene hydrothiolation. In addition, this protocol describes the preparation of vinyl-sulfide-tethered peptides using in-solution intramolecular thiol-yne hydrothiolation between amino acids that possess alkene/alkyne side chains and cysteine residues at i, i+4 positions. Linear peptides were synthesized using a standard Fmoc-based solid-phase peptide synthesis (SPPS). Thiol-ene hydrothiolation is carried out using either an intramolecular thio-ene reaction or an intermolecular thio-ene reaction, depending on the peptide length. In this research, an intramolecular thio-ene reaction is carried out in the case of shorter peptides using on-resin deprotection of the trityl groups of cysteine residues following the complete synthesis of the linear peptide. The resin is then set to UV irradiation using photoinitiator 4-methoxyacetophenone (MAP) and 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propanone (MMP). The intermolecular thiol-ene reaction is carried out by dissolving Fmoc-Cys-OH in an N,N-dimethylformamide (DMF) solvent. This is then reacted with the peptide using the alkene-bearing residue on resin. After that, the macrolactamization is carried out using benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop), 1-hydroxybenzotriazole (HoBt), and 4-Methylmorpholine (NMM) as activation reagents on the resin. Following the macrolactamization, the peptide synthesis is continued using standard SPPS. In the case of the thio-yne hydrothiolation, the linear peptide is cleaved from the resin, dried, and subsequently dissolved in degassed DMF. This is then irradiated using UV light with photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA). Following the reaction, DMF is evaporated and the crude residue is precipitated and purified using high-performance liquid chromatography (HPLC). These methods could function to simplify the generation of thioether-tethered cyclic peptides due to the use of the thio-ene/yne click chemistry that possesses superior functional group tolerance and good yield. The introduction of thioether bonds into peptides takes advantage of the nucleophilic nature of cysteine residues and is redox-inert relative to disulfide bonds.

We present a protocol for the construction of thioether/vinyl sulfide-tethered helical peptides using photo-induced thiol-ene/thiol-yne hydrothiolation.

헬리컬 펩 티 드를 통해 사진 유도 Thiol-ene 또는 yne Hydrothiolation Thioether/비닐 황 화물-곁에 건설

Here, we describe a detailed protocol for the preparation of thioether-tethered peptides using on-resin intramolecular/intermolecular thiol-ene ...

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 ...

Synthesis and Bioconjugation of Thiol-Reactive Reagents for the Creation of Site-Selectively Modified Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. Yet maleimide-based conjugates display limited stability in vivo because the succinimidyl thioether linkage can undergo a retro-Michael reaction. This, of course, can lead to the release of the radioactive payload or its exchange with thiol-bearing biomolecules in circulation. Both of these processes can produce elevated activity concentrations in healthy organs as well as decreased activity concentrations in target tissues, resulting in reduced imaging contrast and lower therapeutic ratios. In 2018, we reported the creation of a modular, stable, and easily accessible phenyloxadiazolyl methyl sulfone reagent &#8212; dubbed &#8216;PODS&#8217; &#8212; as a platform for thiol-based bioconjugations. We have clearly demonstrated that PODS-based site-selective bioconjugations reproducibly and robustly create homogenous, well-defined, highly immunoreactive, and highly stable radioimmunoconjugates. Furthermore, preclinical experiments in murine models of colorectal cancer have shown that these site-selectively labeled radioimmunoconjugates exhibit far superior in vivo performance compared to radiolabeled antibodies synthesized via maleimide-based conjugations. In this protocol, we will describe the four-step synthesis of PODS, the creation of a bifunctional PODS-bearing variant of the ubiquitous chelator DOTA (PODS-DOTA), and the conjugation of PODS-DOTA to the HER2-targeting antibody trastuzumab.

In this protocol, we will describe the synthesis of PODS, a phenyoxadiazolyl methyl sulfone-based reagent for the site-selective attachment of cargos to the thiols of biomolecules, particularly antibodies. In addition, we will describe the synthesis and characterization of a PODS-bearing bifunctional chelator and its conjugation to a model antibody.

합성 및 Bioconjugation의 Thiol 반응 시 약 사이트에 선택적으로의 창조에 대 한 수정 Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...

Synthesis and Calibration of Phosphorescent Nanoprobes for Oxygen Imaging in Biological Systems

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood or interstitial fluid); 2) the object is illuminated with light of appropriate wavelength in order to excite the probe into its triplet state; 3) the emitted phosphorescence is collected, and its time course is analyzed to yield the phosphorescence lifetime, which is converted into the oxygen concentration (or partial pressure, pO2). The probe must not interact with the biological environment and in some cases to be 4) excreted from the medium upon the measurement completion. Each of these steps imposes requirements on the molecular design of the phosphorescent probes, which constitute the only invasive component of the measurement protocol. Here we review the design of dendritic phosphorescent nanosensors for oxygen measurements in biological systems. The probes consist of Pt or Pd porphyrin-based polyarylglycine (AG) dendrimers, modified peripherally with polyethylene glycol (PEG's) residues. For effective two-photon excitation, termini of the dendrimers may be modified with two-photon antenna chromophores, which capture the excitation energy and channel it to the triplet cores of the probes via intramolecular FRET (F&ouml;rster Resonance Energy Transfer). We describe the key photophysical properties of the probes and present detailed calibration protocols.

We present principles of oxygen measurements by phosphorescence quenching and review design of porphyrin-based dendritic nanosensors for oxygen imaging in biological systems.

생물 학적 시스템에서 산소 이미징에 대한 인광을 발하는 나노 프로브의 합성 및 교정

Oxygen measurement by phosphorescence quenching [1, 2] consists of the following steps: 1) the probe is delivered into the medium of interest (e.g. blood ...

생물학

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

Methine-bridged conjugated bicyclic aromatic compounds are common constituents of a range of biologically relevant molecules such as porphyrins, dipyrrinones, and pharmaceuticals. Additionally, restricted rotation of these systems often results in highly to moderately fluorescent systems as observed in 3H,5H-dipyrrolo[1,2-c:2',1'-f]pyrimidin-3-ones, xanthoglows, pyrroloindolizinedione analogs, BODIPY analogs, and the phenolic and imidazolinone ring systems of Green Fluorescent Protein (GFP). This manuscript describes an inexpensive and operationally simple method of performing a Claisen-Schmidt condensation to generate a series of fluorescent pH dependent pyrazole/imidazole/isoindolone dipyrrinone analogs. While the methodology illustrates the synthesis of dipyrrinone analogs, it can be translated to produce a wide range of conjugated bicyclic aromatic compounds. The Claisen-Schmidt condensation reaction utilized in this method is limited in scope to nucleophiles and electrophiles that are enolizable under basic conditions (nucleophile component) and non-enolizable aldehydes (electrophile component). Additionally, both the nucleophilic and electrophilic reactants must contain functional groups that will not inadvertently react with hydroxide. Despite these limitations, this methodology offers access to completely novel systems that can be employed as biological or molecular probes.

The Claisen-Schmidt condensation reaction is an important methodology for the generation of methine-bridged conjugated bicyclic aromatic compounds. Through utilizing a base-mediated variant of the aldol reaction, a range of fluorescent and/or biologically relevant molecules can be accessed through a generally inexpensive and operationally simple synthetic approach.