TWI552953B - 石墨烯奈米帶前驅物及適用於製備彼等之單體 - Google Patents
石墨烯奈米帶前驅物及適用於製備彼等之單體 Download PDFInfo
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- TWI552953B TWI552953B TW101139808A TW101139808A TWI552953B TW I552953 B TWI552953 B TW I552953B TW 101139808 A TW101139808 A TW 101139808A TW 101139808 A TW101139808 A TW 101139808A TW I552953 B TWI552953 B TW I552953B
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Description
本發明係關於石墨烯奈米帶前驅物，係關於可藉由氧化脫氫環化(分子內Scholl反應)自其獲得之石墨烯奈米帶，係關於製備該等石墨烯奈米帶前驅物之方法，係關於適用於製備該等石墨烯奈米帶前驅物之單體，且係關於製備該等單體之方法。
石墨烯奈米帶(GNR)係來自石墨烯結構之經界定部分。其由以蜂巢形狀佈置之sp2雜化碳原子單層帶組成且具有高長度：寬度之邊長比，使得其係準一維碳多晶型物。因該等帶之低寬度與其長度相關，故在石墨烯奈米帶中邊緣結構對石墨烯之電子性質之影響不可忽視。藉助邊緣結構可以受控方式影響石墨烯奈米帶之電子性質。
石墨烯自身已用於有機電子器件，例如在場效電晶體中作為透明電極材料或作為活性材料。然而，石墨烯不具有天然帶隙，從而無法在電子器件電路中用作半導體。然而，理論模型已顯示，藉由控制寬度及邊緣結構可在石墨烯奈米帶中獲得合成帶隙。為獲得該等半導電石墨烯奈米帶，需要具有「扶手椅」邊緣結構且寬度<10 nm之經界定結構之無缺陷石墨烯帶。迄今為止尚未獲得該等無缺陷石墨烯帶。
不可藉由諸如以下「自上而下」法來控制所獲得石墨烯奈米帶之大小及邊緣結構：石墨烯氧化物之還原(S.
Stankovich,D.Dikin,R.Piner,K.Kohlhaas,A.Kleinhammes,Y.Jia,Y.Wu,S.Nguyen,R.Ruoff,Carbon 2007,45,1558)、微影(M.Han,B.Özyilmaz,Y.Zhang,P.Kim,Phys.Rev.Lett,2007,98,206805；Z.Chen,Y.Lin,M.Rooks,P.Avouris,Physica E,2007,40,228)、碳奈米管之解壓(a)L.Jiao,X.Wang,G.Diankov,H.Wang,H.Dai,Nat.Nanotechnol.2010,5,321；b)D.Kosynkin,A.Higginbotham,A.Sinitskii,J.Lomeda,A.Dimiev,B.Price,J.Tour,Nature 2009,458,872)或石墨烯之機械剝離(X.Li,X.Wang,L.Zhang,S.Lee,H.Dai,Science 2008,219,1229)。相反，有機「自下而上」合成允許在原子層面上之結構控制且因此適用於製造具有精確經界定結構之GNR。
X.Yang,X.Dou,A.Rouhanipour,L.Zhi,H.Rader,K.Miillen,J.Am.Chem.Soc.2008,130,4216揭示根據下文反應圖1藉由適宜聚合物前驅物之脫氫環化來製造石墨烯奈米帶。
該合成係基於研發在反應步驟中藉由氧化脫氫環化(分子內Scholl反應)轉化成二維石墨烯結構之特製聚合物前驅物。然而，無法達成完全脫氫環化，因此，因存在缺陷而不能進行電子性質之研究。
反應圖2顯示聚合得到聚合物前驅物。
在Suzuki縮聚期間單體之強立體位阻導致聚合物之最大長度為約10 nm，此乃因單體3中之碘官能基被鄰位的兩個苯基顯著屏蔽，從而使得偶合反應更困難。另外，碳-碘
鍵可能易於熱斷裂，且導致鏈終止。同時，在聚合物中存在因重疊烷基導致的空間位阻，在後續脫氫環化步驟中，其會阻礙毗鄰該等基團之芳基-芳基鍵之形成並導致不完全脫氫環化。已發現另一缺點係聚合物主鏈之聚(對-伸苯基)結構，其僅允許沿聚合物鏈具有低程度之撓性。此會導致在獲得相對較高分子量之前分子之聚集及沈澱增強，即使在聚合期間。
另外，在A2+B2型聚合反應之情形下，該等單體必須以精確化學計量量使用，此乃因以其他方式僅達成低程度之聚合。
本發明之目的係提供製造石墨烯奈米帶之方法及不具有先前技術缺點之適宜石墨烯奈米帶前驅物。本發明之具體目的係提供產生具有「扶手椅」邊緣結構之無缺陷石墨烯奈米帶之石墨烯奈米帶前驅物。
該目的係藉由以下達成：包含通式(I)之重複單元之石墨烯奈米帶前驅物
其中R1、R2各自係H；鹵素；-OH；-NH2；-CN；-NO2；烴基，其具有1至40個碳原子且可為直鏈或具支鏈、飽和或不飽和且經鹵素(F、Cl、Br、I)、-OH、-NH2、-CN及/或-NO2單取代或多取代，其中一或多個CH2基團亦可經-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代，其中R係視情況經取代之C1-C40-烴基；或視情況經取代之芳基、烷基芳基或烷氧基芳基，及藉由氧化脫氫環化可自其獲得之石墨烯奈米帶。
該目的亦係藉由以下達成：製備石墨烯奈米帶前驅物之方法，其包含通式(II)之單體單元之Yamamoto偶合反應
其中R1、R2各自係H；鹵素；-OH；-NH2；-CN；-NO2；或烴基，其具有1至40個碳原子且可為直鏈或具支鏈、飽和或不飽和且經鹵素(F、Cl、Br、I)、-OH、-NH2、-CN及/或-NO2單取代或多取代，其中一或多個CH2基團亦可經-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代，其中R係視情況經取代之C1-C40-烴基；或視情況經取代之芳基、烷基芳基或烷氧基芳基，且X係鹵素、三氟甲磺酸酯或重氮及通式(H)之單體單元自身。
一般而言，R1、R2各自係H或可經指定取代基單-至五取代之飽和或單-至五烯系及/或炔系不飽和烴基。
較佳地，R1、R2係H或可經指定取代基單-至五取代之直鏈或具支鏈飽和烴基。
較佳地，R1、R2各自獨立地係氫、C1-C30-烷基、C1-C30-
烷氧基、C1-C30-烷硫基、C2-C30-烯基、C2-C30-炔基、C1-C30-鹵烷基、C2-C30-鹵烯基及鹵炔基，例如C1-C30-全氟烷基。
C1-C30-烷基可為直鏈或(若可能)具支鏈。
實例係甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、1,1,3,3-四甲基戊基、正己基、1-甲基己基、1,1,3,3,5,5-六甲基己基、正庚基、異庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、1,1,3,3-四甲基丁基及2-乙基己基、正壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、二十烷基、二十一烷基、二十二烷基、二十四烷基或二十五烷基。
C1-C30-烷氧基係直鏈或具支鏈烷氧基，例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、戊氧基、異戊氧基或第三戊氧基、庚氧基、辛氧基、異辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基及十八烷氧基。
術語「烷硫基」意指與烷氧基相同者，只是醚鍵中之氧原子經硫原子替代。
C2-C30-烯基係直鏈或具支鏈，例如乙烯基、烯丙基、甲基烯丙基、異丙烯基、2-丁烯基、3-丁烯基、異丁烯基、正戊-2,4-二烯基、3-甲基-丁-2-烯基、正辛-2-烯基、正十
二-2-烯基、異十二烯基、正十二-2-烯基或正十八-4-烯基。
C2-C30-炔基係直鏈或具支鏈，例如，乙炔基、1-丙炔-3-基、1-丁炔-4-基、1-戊炔-5-基、2-甲基-3-丁炔-2-基、1,4-戊二炔-3-基、1,3-戊二炔-5-基、1-己炔-6-基、順式-3-甲基-2-戊烯-4-炔-1-基、反式-3-甲基-2-戊烯-4-炔-1-基、1,3-己二炔-5-基、1-辛炔-8-基、1-壬炔-9-基、1-癸炔-10-基或1-二十四炔-24-基。
C1-C30-全氟烷基係具支鏈或不具支鏈，例如-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-(CF2)3CF3或-C(CF3)3。
術語「鹵烷基、鹵烯基及鹵炔基」意指部分地或完全經鹵素取代之烷基、烯基及炔基。
芳基通常係C6-C30-芳基且視情況可經取代，例如，苯基、4-甲基苯基、4-甲氧基苯基、萘基、聯苯基、聯三苯基、芘基、茀基、菲基、蒽基、四醯基、五醯基及六醯基。
較佳地，X=Cl或Br。更佳地，R1、R2各自係H或C8-C30-烷基，尤其H或C10-C26-烷基。
較佳地，R2=H。
藉助自本發明單體單元(II)進行之Yamamoto偶合反應，可製造通常具有3個至100個且較佳5個至50個重複單元(I)之石墨烯奈米帶。另外，Yamamoto聚合反應不像A2+B2型聚合反應一樣化學計量敏感。
在形成石墨烯奈米帶前驅物之聚合步驟期間及在該前驅物之後續脫氫環化以得到石墨烯奈米帶期間，石墨烯奈米帶前驅物分子之具角度主鏈減小立體位阻。此使得在空間上要求引入烷基，從而另外產生增加之溶解性。在聚合期間，具有相對較高撓性之具角度聚合物主鏈之相對較高程度之扭轉抑制分子聚集，因此可達成相對較高分子量。
用於製備通式(II)之單體之合成反應圖顯示於反應圖3中。
自1,3-二(聯苯-3-基)丙-2-酮7(其已包含該兩個撓性間-
聯苯單元)進行與4,4'-二鹵代二苯乙二酮之Knoevenagel縮合，引入用於隨後Yamamoto聚合之兩個鹵素官能基以獲得四芳基環戊二烯酮8。藉由與視情況官能化之二苯乙炔10之Diels-Alder環加成使環戊二烯酮8轉化，得到單體6。此反應可在微波反應器中實施。
石墨烯奈米帶前驅物係對應反應圖4在鎳觸媒之存在下藉由Yamamoto聚合自單體6合成。適宜觸媒系統包含存於甲苯/DMF混合物(作為溶劑)中之Ni(COD)2、1,5-環辛二烯及2,2'-聯吡啶。所形成聚合物可藉由添加氯苯或溴苯進行「封端」，即可將末端鹵素官能基更換為苯基。
得到石墨烯奈米帶之石墨烯奈米帶前驅物11之脫氫環化可借助分子內Scholl反應使用(例如)氯化鐵(III)作為路易士酸(Lewis acid)及氧化劑來實施。
一般而言，所獲得石墨烯奈米帶之分子量係2000至100 000，較佳地4000至50 000，該等分子量可借助GPC測定。
石墨烯奈米帶亦可於金屬表面上製造。此係藉由昇華將該單體沈積至該表面上來實施。藉此產生雙自由基，該等雙自由基隨溫度增加而聚合，得到石墨烯奈米帶前驅物。在最後步驟中，對基板之進一步熱處理達成脫氫環化，得到最終石墨烯奈米帶(參見Cai,J.等人；Nature 466,470-473(2010))。
藉由下文實例詳細說明本發明。
該等圖式顯示：
圖1所合成單體6a-c之疊加MALDI-TOF質譜；圖2所合成單體6a-c之1H NMR光譜之相關芳族區域；圖3聚合物前驅物11a-c之MALDI-TOF質譜；圖4 GNR 12b之拉曼光譜(Raman spectrum)；圖5 GNR 12a、b之IR光譜。
用於製備通式(II)6a至6c之單體之合成反應圖顯示於反應圖5中。
使用四丁基氫氧化銨作為鹼自1,3-二(聯苯-3-基)丙-2-酮7(其已包含該兩個撓性間-聯苯單元)進行與4,4'-二溴二苯乙二酮9a或4,4'-二氯二苯乙二酮9b之Knoevenagel縮合引入用於隨後的Yamamoto聚合之兩個鹵素官能基。四芳基環戊二烯酮8a及8b無法藉由管柱層析自反應物去除，但該等產物能夠選擇性地自DCM沈澱於甲醇中。因此，獲得呈紫色固體形式之8a(產率為77%)及8b(53%)。在最後反應步驟中，引入增溶基團並藉由與官能化二苯乙炔之Diels-Alder環加成使環戊二烯酮轉化，得到目標化合物。由於高立體要求，故此反應必須在微波反應器中在220℃及300瓦特下並經24 h反應時間實施。在利用矽膠管柱層析純化並反覆再沈澱後，借助循環GPC來純化所有單體。儘管產率相應降低，但此高純度對於在聚合中達成高分子量係必需的。因此獲得呈無色固體形式之不含烷基之單體6a，產率為40%。8b與4,4'-二(十二烷基)二苯乙炔10b加成得到單體6b，產率為56%，且與4,4'-雙(2-癸基十四烷基)二苯乙炔10c反應得到單體6c，產率為41%。該兩種烷基化產物均呈無色油狀物形式獲得。
在80℃下向2.84 g 4,4'-二溴二苯乙二酮(7.73 mmol)及
2.80 g 1,3-二(聯苯-3-基)丙-2-酮(7,7.73 mmol)於30 ml第三丁醇中之經脫氣溶液中添加甲醇化四丁基氫氧化銨溶液(1 M,2.84 ml,2.84 mmol)。在80℃下將反應溶液攪拌20分鐘且然後藉由添加水終止。用二氯甲烷實施萃取3次，並用飽和氯化鈉溶液洗滌所收集之有機相並經硫酸鎂乾燥，然後在減壓下蒸餾出溶劑。藉由管柱層析(矽膠，洗脫液：具有20% DCM之己烷)來純化粗產物並得到2.85 g呈紫色蠟形式之四芳基環戊二烯酮8a(53%,4.10 mmol)。元素分析量測值：C 70.5；H 3.3%(C41H26Br2O之計算值：C 70.9；H 3.8%)；1H NMR(700 MHz,d8-THF)δ=7.51-7.49(m,4H,CH),7.49-7.46(m,4H,CH),7.41(dd,J=8.2,1.1 Hz,4H,CH),7.36(t,J=7.8 Hz,4H,CH),7.32(t,J=8.0 Hz,2H,CH),7.29-7.25(m,2H,CH),7.25-7.22(m,2H,CH),7.01-6.99(m,4H,CH)；13C NMR(175 MHz,d8-THF)δ=154.28,141.92,141.83,133.58,132.72,132.34,132.30,132.12,129.99,129.89,129.71,129.53,128.26,127.80,127.21,126.74,123.92；MS(FD,8 kV)：m/z(%)：693.8(100)[M+](C41H26Br2O之計算值：694.0)；Rf(具有6%乙酸乙酯之己烷)=0.47。
在微波反應器中在300瓦特功率及7巴最大壓力下將300 mg 2,5-二([1,1'-聯苯]-3-基)-3,4-雙(4-溴-苯基)環戊-2,4-二烯酮(8a,0.432 mmol)及77.0 mg 4,4'-二溴二苯乙炔(0.432
mmol)於3 ml二苯基醚中之經脫氣溶液加熱至230℃，保持3×12 h。在冷卻至室溫後，用己烷稀釋反應溶液並藉由管柱層析(二氧化矽，具有6%乙酸乙酯之己烷)來純化。在借助循環GPC純化並在高真空下乾燥後，獲得145 mg呈無色晶體形式之單體6a(40%,0.172 mmol)。元素分析量測值：C 76.7；H 3.1%(C54H36Br2之計算值：C 76.8；H 4.3%)；1H NMR(700 MHz,d8-THF)δ=7.30-7.25(m,4H,CH),7.23-7.17(m,6H,CH),7.13(d,J=1.5 Hz,1H,CH),7.12-7.11(m,1H,CH),7.11-7.09(m,4H,CH),7.09-7.06(m,2H,CH),6.95(s,1H,CH),6.94(br s,2H,CH),6.93(s,1H,CH),6.91(t,J=4.1 Hz,2H,CH),6.89(d,J=8.0 Hz,2H,CH),6.85(d,J=7.0 Hz,4H,CH),6.83(d,J=2.0 Hz,2H,CH),6.81(d,J=1.4 Hz,1H,CH),6.79(d,J=8.3 Hz,2H,CH),6.78(s,1H,CH)；13C NMR(125 MHz,d2-TCE)δ=141.05,140.74,140.20,140.00,139.44,139.03,138.52,133.03,132.92,131.30,131.15,130.26,129.92,129.85,128.42,127.17,126.87,126.62,126.52,125.20,124.15,120.18,119.51；MS(MALDI-TOF)：m/z(%)：845.1(100)[M+](C54H36Br2之計算值：844.1)；Rf(具有6%乙酸乙酯之己烷)=0.40；m.p.(℃)：在>400℃時分解。
在80℃下向940 mg 4,4'-二氯二苯乙二酮(3.37 mmol)及1.22 g 1,3-二(聯苯-3-基)丙-2-酮(7,3.37 mmol)於20 ml第
三丁醇中之經脫氣溶液中添加甲醇化四丁基氫氧化銨溶液(1 M,1.7 ml,1.7 mmol)。在80℃下將反應溶液攪拌20分鐘，且然後藉由添加水終止反應。用二氯甲烷將混合物萃取3次並用飽和氯化鈉溶液洗滌所收集之有機相並經硫酸鎂乾燥，然後在減壓下蒸餾出溶劑。藉由管柱層析(矽膠，洗脫液：具有20% DCM之己烷)來純化粗產物並得到1.56 g呈淡紫色固體形式之四芳基環戊二烯酮8b(77%,2.58 mmol)。元素分析量測值：C 81.3；H 3.3%(C41H26Cl2O之計算值：C 81.3；H 4.3%)；1H NMR(700 MHz,d8-THF)δ=7.52(s,2H,CH),7.50(d,J=7.8 Hz,2H,CH),7.42(d,J=7.2 Hz,4H,CH),7.36(t,J=7.7 Hz,4H,CH),7.32(m,6H,CH),7.27(t,J=7.3 Hz,2H,CH),7.23(d,J=7.8 Hz,2H,CH),7.06(d,J=8.5 Hz,4H,CH)；13C NMR(175 MHz,d8-THF)δ=199.86,154.28,141.91,141.82,135.61,133.14,132.14,132,10,129.98,129.90,129.70,129.69,129.52,128.27,127.78,127.20,126.73；MS(MALDI-TOF)：m/z(%)：604.6(100)[M+](C41H26Cl2O之計算值：604.1)；Rf(具有10%乙酸乙酯之己烷)=0.47。
在微波反應器中在300瓦特功率及7巴最大壓力下將1.84 g 2,5-二([1,1'-聯苯]-3-基)-3,4-雙(4-氯-苯基)環戊-2,4-二烯酮(8b,3.03 mmol)及1.72 g 4,4'-二(十二烷基)二苯乙炔(3.34 mmol)於12 ml二苯基醚及5 ml碳酸丙二酯中之經脫
氣溶液加熱至230℃，保持2×12 h。在冷卻至室溫後，用己烷稀釋反應溶液並藉由管柱層析(二氧化矽，具有6%乙酸乙酯之己烷)來純化。在借助循環GPC純化並在高真空下乾燥後，獲得1.85 g呈無色油狀物形式之單體6b(56%,1.69 mmol)。元素分析量測值：C 85.6；H 7.9%(C78H84Cl2之計算值：C 85.8；H 7.8%)；1H NMR(700 MHz,d8-THF)δ=7.27(dt,J=7.7,4.0 Hz,4H,CH),7.22-7.16(m,6H,CH),7.10(d,J=10.0 Hz,4H,CH),6.94(t,J=7.7 Hz,4H,CH),6.91(s,2Hv),6.88(d,J=8.4 Hz,2H,CH),6.87-6.81(m,2H,CH),6.81-6.77(m,2H,CH),6.77-6.70(br m,6H,CH),6.66(d,J=7.5 Hz,2H,CH),2.41-2.28(m,4H,α-CH2),1.44-1.34(m,4H,(β-CH2),1.34-1.03(m,36H,-CH2-),0.89(t,J=6.9 Hz,6H,-CH3)；13C NMR(175 MHz,d8-THF)δ=142.44,142.42,142.27,141.88,141.74,140.76,140.74,140.68,140.59,140.56,140.14,140.10,139.09,139.05,134.18,134.14,134.06,134.01,132.56,132.50,132.47,132.30,132.26,131.69,131.41,129.37,128.20,128.07,127.90,127.88,127.84,127.81,127.80,127.74,125.14,125.12,36.36,36.33,33.06,32.37,32.34,30.85,30.81,30.77,30.75,30.61,30.60,30.51,30.00,29.98,25.94,25.82,23.74,14.62；MS(MALDI-TOF)：m/z(%)：1091.0(100)[M+](C78H84Cl2之計算值：1090.6)；Rf(具有6%乙酸乙酯之己烷)=0.65。
在微波反應器中在300瓦特功率及7巴最大壓力下將636 mg 2,5-二([1,1'-聯苯]-3-基)-3,4-雙(4-氯苯基)環戊-2,4-二烯酮(8b,1.05 mmol)及895 mg 4,4'-雙(2-癸基十四烷基)二苯乙炔(1.05 mmol)於10 ml二苯基醚中之經脫氣溶液加熱至230℃，保持2×12 h。在冷卻至室溫後，用己烷稀釋反應溶液並藉由管柱層析(二氧化矽，具有6%乙酸乙酯之己烷)來純化。在借助循環GPC純化並在高真空下乾燥後，獲得613 mg呈無色油狀物形式之單體6c(41%,0.429 mmol)。元素分析量測值：C 86.0；H 9.7%(C102H132Cl2之計算值：C 85.8；H 9.3%)；1H NMR(700 MHz,d8-THF)δ=7.29-7.25(m,4H,CH),7.20(m,6H,CH),7.14(s,1H,CH),7.11(d,J=10.0 Hz,3H,CH),6.95-6.88(m,9H,CH),6.85(d,J=8.4 Hz,1H,CH),6.81(d,J=8.0 Hz,1H,CH),6.79(d,J=7.8 Hz,2H,CH),6.77(d,J=7.7 Hz,1H,CH),6.73(d,J=7.8 Hz,2H,CH),6.69(t,J=7.6 Hz,2H,CH),6.64(d,J=7.9 Hz,2H,CH),2.33-2.24(m,4H,α-CH2),1.44-1.37(m,2H,β-CH2),1.35-0.95(br m,80H,-CH2-),0.89(m,12H,-CH3)；13C NMR(175 MHz,d8-THF)δ=142.43,142.41,142.20,142.18,141.94,141.77,140.69,140.65,140.55,140.52,140.10,140.07,139.61,139.08,134.13,134.04,133.98,132.48,132.31,132.13,131.70,131.37,129.41,128.67,128.53,128.21,128.07,127.87,127.77,125.08,40.92,40.61,33.94,33.86,33.81,33.08,33.06,
31.20,31.12,31.10,30.89,30.86,30.82,30.54,30.52,27.49,27.45,25.93,25.82,23.76,23.75,14.63；MS(MALDI-TOF)：m/z(%)：1427.8(100)[M+](C102H132Cl2之計算值：1428.0)；Rf(具有6%乙酸乙酯之己烷)=0.76。
圖1顯示所合成單體6a-c之疊加MALDI-TOF質譜。在全部三種情形下均能夠獲得呈純淨形式之產物且能夠確保不再存在隨後的聚合期間會導致鏈生長終止之副產物。單體之精確結構係藉由1H NMR光譜來證實。
圖2顯示以d8-THF記錄之單體6a-c之1H NMR光譜之相關芳族區域(700 MHz,RT)。單獨解析單體6a-c之1H NMR光譜可能具有難度，此乃因所有34個至36個芳族質子均展示極類似之化學偏移。信號係在6.6 ppm至7.3 ppm之窄範圍內，且一些經疊加。借助DOSY(擴散排序譜)，可測定樣品中分子之擴散性質，且COSY實驗可測定NMR中共軛質子之信號間之耦合。
在證實單體6a-c之結構及純度後，根據反應圖6藉由Yamamoto聚合來合成相應聚合物。
反應圖6
反應圖6顯示石墨烯奈米帶前驅物11a-c之合成，此藉由在甲苯/DMF中利用Ni(COD)2、1,5-環辛二烯及2,2'-聯吡啶催化二鹵代單體6a-c之Yamamoto聚合來達成。產率為(i)84%、(ii)86%、(iii)67%。由於催化活性鎳(0)試劑在Yamamoto縮聚中對水及氧極為敏感，故所有單體單元6均在其用於聚合之前在高真空下乾燥。在手套箱中在氬氣氛圍下稱取由59.4 mg Ni(COD)2、23.4 mg 1,5-環辛二烯及33.7 mg 2,2'-聯吡啶(各0.216 mmol)組成之觸媒混合物並在微波兼容玻璃反應容器中與溶劑一起製備，用具有隔片之氣密性鋁蓋密封並免受任何入射光。使用微波反應器來實施反應獲得明顯增加之反應速率及高於溶劑沸點之反應溫
度之優點。在60℃下將觸媒熱活化20分鐘後，將0.09 mmol單體於1 ml無水甲苯中之經脫氣溶液透過隔片引入反應容器中，並在300瓦特微波功率及80℃下實施聚合歷時10小時之時間段。使用約50 mg/ml之單體濃度來促進高分子量之達成。為將聚合物封端，最後添加溴苯/氯苯於甲苯中之經脫氣溶液(0.5 ml，0.01莫耳濃度)，並將混合物再加熱至80℃，保持20分鐘。為純化產物及去除觸媒殘餘物，將反應溶液逐滴添加至HCl/甲醇混合物中並攪拌過夜。在離心機中去除所得沈澱物並在甲醇中用THF反覆再沈澱，然後濾出並在減壓下乾燥。獲得呈無色固體形式之不含烷基之聚合物11a及具有十二烷基鏈之11b，產率為84%至86%。只有藉由引入具支鏈2-癸基十四烷基才能使熔點降低至聚合物11c在室溫下呈無色油狀物形式存在之程度。在後續脫氫環化以產生相應GNR之前，藉由手動製備型GPC分餾來去除低分子量寡聚物。此係可能的，因全部三種聚合物完全可溶於常見有機溶劑(例如THF、DCM或甲苯)中。
所用單體係76.0 mg 1,2-雙(4-溴苯基)-3,6-雙(聯苯-3-基)-4,5-二苯基苯(6a,0.09 mmol)。在反應結束並冷卻至室溫後，已形成無色沈澱物。在純化粗產物後，獲得43.7 mg呈無色固體形式之聚合物11a(84%)。GPC分析：Mn=0.11×104 g/mol，Mw=0.15×104 g/mol，多分散度D=1.35(UV檢測器，PS標準品)，DSC(℃)：無相變。
所用單體係98.3 mg 1,2-雙(4-溴苯基)-3,6-雙(聯苯-3-基)-4,5-雙(4-十二烷基苯基)苯(6b,0.09 mmol)。在反應結束並冷卻至室溫後，反應溶液已變成深褐色，且在燒瓶壁上存在黑色沈澱物。在純化粗產物後，獲得79.0 mg呈無色固體形式之聚合物11b(86%)。GPC分析：Mn=0.93×104 g/mol，Mw=1.25×104 g/mol，多分散度D=1.34(UV檢測器，PS標準品)，DSC(℃)：無相變。
所用單體係128.6 mg 1,2-雙(4-溴苯基)-3,6-雙(聯苯-3-基)-4,5-雙(4-(2-癸基十四烷基)十二烷基苯基)苯(6c,0.09 mmol)。在反應結束並冷卻至室溫後，反應溶液已變成深褐色，且在燒瓶壁上存在黑色沈澱物。在純化粗產物後，獲得81.9 mg呈無色油狀物形式之聚合物11c(67%)。GPC分析：Mn=0.35×104 g/mol，Mw=0.48×104 g/mol，多分散度D=1.37(UV檢測器，PS標準品)，DSC(℃)：無相變。
藉由MALDI-TOF MS及GPC分析來測定於聚合物11a-c中獲得之分子量。由於無適宜標準品用於GPC分析，故使用聚苯乙烯標準品，此係由於該等聚合物之具角度主鏈。MALDI-TOF MS經受因樣品之多分散度而不可檢測高分子量物質之限制。因此，此處獲得之數據僅容許推測樣品中之最小分子量。針對聚合物前驅物11a-c記錄之MALDI-TOF質譜再現於圖3中。
借助MALDI-TOF MS之聚合物11a-c之分析顯示，在所
有情形下均觀察到極規則之信號圖案，因此在該等信號之間隔與各別重複單元之經計算分子量之間存在高度對應性。在11a之情形下，強信號歸屬於完全脫溴產物。弱信號因在電離期間銀離子之吸附而產生，且在反射器模式中未觀察到。可檢測到至多5000 g/mol之分子量，其對應於7個重複單元之最大值。在具有十二烷基鏈之聚合物11b之情形下，檢測到至多20 000 g/mol之分子量(19個重複單元)。在聚合物11c之情形下，檢測到莫耳質量至多10 000 g/mol之7個重複單元。
由於全部三種聚合物11a-c(除烷基外)均具有相同重複單元，故可容易地將分子量轉化成鏈長度。此長度對應於在脫氫環化後GNR隨後的縱向尺寸。對於具有十二烷基鏈之石墨烯奈米帶前驅物11b，20 000 g/mol之莫耳質量對應於隨後的寬度為2.1 nm且長度為約12 nm之石墨烯帶(約1.2 nm/重複單元)。
根據反應圖7得到相應GNR 12a-c之聚合物前驅物11a-c之脫氫環化係借助分子內Scholl反應使用氯化鐵(III)作為路易士酸及氧化劑來實施。
通常，該反應係以1 mg/ml之極低聚合物濃度在未經穩定化之二氯甲烷中實施以防止發生分子內芳基-芳基偶
合。在整個反應時間內用氬氣流使反應溶液脫氣以驅除氧氣及所形成之HCl。在反應開始時，快速添加呈存於硝基甲烷中之濃溶液形式之每個所形成鍵6當量之氯化鐵(III)(每個重複單元90當量)，並在室溫下將混合物攪拌3天。在結束脫氫環化後，用甲醇沈澱GNR並進一步純化。
獲得呈黑色固體之不含烷基之GNR 12a及具有十二烷基之GNR 12b，產率為64%及98%，其不可溶於諸如甲苯、THF、四氯乙烷或氯仿等標準有機溶劑中。在石墨烯帶之寬度為2.1 nm之情況下，π-π相互作用非常強烈，使得在12b之情形下每個重複單元之兩個十二烷基不足以防止聚集。因此，處理時，藉由用THF及甲醇實施索氏萃取(Soxhlet extraction)來清除粗產物之所有可溶性雜質，且最後在高真空下乾燥。相反，獲得可溶於諸如THF或甲苯等標準有機溶劑中之呈黑色固體形式之具有2-癸基十四烷基鏈之GNR 12c，產率為81%。因此，藉由在甲醇中自THF反覆再沈澱來實施純化且隨後用丙酮實施索氏萃取，以去除雜質、副產物及無機殘餘物。
使50 mg聚合物前驅物11a與1.12 g FeCl3(6.87 mmol，溶解於4 ml硝基甲烷中)反應。在3天反應時間後，已形成黑色沈澱物，在離心機中將其去除。對於純化而言，在每一情形下均用THF及甲醇對粗產物實施2天索氏萃取，且最後在高真空下乾燥。因此，獲得呈黑色不可溶固體形式之32.0 mg GNR 12a(64%)。DSC(℃)：無相變。
使76.6 mg聚合物前驅物11b與1.10 g FeCl3(6.76 mmol，溶解於3.5 ml硝基甲烷中)反應。在3天反應時間後，已形成黑色沈澱物，在離心機中將其去除。對於純化而言，在每一情形下均用THF及甲醇對粗產物實施2天索氏萃取，且最後在高真空下乾燥。因此，獲得呈黑色不可溶固體形式之72.9 mg GNR 12b(98%)。DSC(℃)：無相變。
使38.11 mg聚合物前驅物11c與410 mg FeCl3(2.53 mmol，溶解於1.3 ml硝基甲烷中)反應。在添加甲醇後，形成黑色沈澱物，在離心機中將其去除並藉由在甲醇中自THF再沈澱且隨後用丙酮實施2天索氏萃取來清除所有雜質、副產物及無機殘餘物。在高真空下乾燥後，獲得呈黑色固體形式之30.2 mg GNR 12c(81%)。DSC(℃)：無相變。
借助拉曼及IR光譜證實GNR 12a-c之完全脫氫環化及無缺陷結構。圖4顯示利用在λ=488 nm處之雷射激發在薄粉末膜中記錄之GNR 12b之拉曼光譜。拉曼光譜允許獲得關於GNR中π-系統之範圍之相關信息，且因此允許計算共軛長度。藉由IR吸收量測，可檢測所有樣品在4050 cm-1處之能帶(其係苯基環之自由旋轉之特性)之存在，且在完全脫氫環化之情形下不再可檢測到。
GNR 12b係唯一在固態未顯示螢光之樣品，且因此允許利用488 nm之雷射激發波長在薄粉末膜上記錄拉曼光譜。
所獲得光譜顯示於圖4中。在1331 cm-1處之特性D能帶及在1579 cm-1處之尖銳G能帶二者均獲得良好的解析度。該等能帶之位置與自文獻得知之證實樣品之石墨烯特徵之石墨烯帶之值高度對應。在多倍該等波數下，亦可發現二階及三階信號。對於GNR 12b之尺寸La之計算，一階D能帶與G能帶之積分(I)之比率藉由式l(D)/l(G)=C(λ)/La轉化。C(λ)係波長依賴性因子，對於λ=488 nm，假定值C(λ)=4.4 nm。因此，經計算尺寸為4.6 nm至4.7 nm，其對應於約8個重複單元且分子量為約8000 g/mol之石墨烯帶。
另外藉由IR光譜證實GNR 12a及12b之脫氫環化之完全性。圖5顯示GNR 12a及12b之IR光譜。在4050 cm-1處之能帶係在每一情形下苯基環自由旋轉之特性，且在聚合物前驅物11a及11b之光譜中清楚地觀察到該能帶(上線)。在脫氫環化結束後，此能帶完全不存在(下線)排除分子中未縮合苯基環之存在，且因此證實完全脫氫環化。
圖1所合成單體6a-c之疊加MALDI-TOF質譜；圖2所合成單體6a-c之1H NMR光譜之相關芳族區域；圖3聚合物前驅物11a-c之MALDI-TOF質譜；圖4 GNR 12b之拉曼光譜(Raman spectrum)；圖5 GNR 12a、b之IR光譜。
Claims (5)
- 一種石墨烯奈米帶前驅物，其包含通式(I)之重複單元
- 一種石墨烯奈米帶，其可藉由使如請求項1之石墨烯奈米帶前驅物在溶液中或在金屬表面上脫氫環化來獲得。
- 一種製備石墨烯奈米帶前驅物之方法，其包含通式(II)之單體之Yamamoto偶合反應
- 一種製備通式(II)之單體之方法，其包含以下步驟：(i)藉由Knoevenagel縮合使1,3-二(聯苯-3-基)丙-2-酮7
- 一種通式(II)之單體，其用於藉由Yamamoto偶合反應來製備石墨烯奈米帶前驅物
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| RU2014120918A (ru) | 2015-12-10 |
| JP2015502415A (ja) | 2015-01-22 |
| SG11201401853QA (en) | 2014-05-29 |
| IN2014CN03432A (zh) | 2015-07-03 |
| KR20150000860A (ko) | 2015-01-05 |
| EP2771309A1 (en) | 2014-09-03 |
| TW201323328A (zh) | 2013-06-16 |
| US20140301936A1 (en) | 2014-10-09 |
| US9434619B2 (en) | 2016-09-06 |
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