CN106750194B - 一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物及其制备方法和用途 - Google Patents
一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物及其制备方法和用途 Download PDFInfo
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- CN106750194B CN106750194B CN201611183051.8A CN201611183051A CN106750194B CN 106750194 B CN106750194 B CN 106750194B CN 201611183051 A CN201611183051 A CN 201611183051A CN 106750194 B CN106750194 B CN 106750194B
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- phenanthroline
- metal complex
- phencd
- imidazole
- dye
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- -1 phenanthroline imidazole derivative Chemical class 0.000 title claims abstract description 35
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 21
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
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- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
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- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 4
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- GBJBDOWMZMXKCD-UHFFFAOYSA-N 2,5-dibromothiophene-3-carbaldehyde Chemical compound BrC1=CC(C=O)=C(Br)S1 GBJBDOWMZMXKCD-UHFFFAOYSA-N 0.000 claims description 3
- GGWLFUNAGOCQPQ-UHFFFAOYSA-N 2-(2,5-dibromothiophen-3-yl)-3-octylimidazo[4,5-f][1,10]phenanthroline Chemical compound BrC=1SC(=CC=1C=1N(C=2C(=C3C=CC=NC3=C3N=CC=CC=23)N=1)CCCCCCCC)Br GGWLFUNAGOCQPQ-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
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- 229960000583 acetic acid Drugs 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
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- ZPMYMUGEJTYYJI-UHFFFAOYSA-N 2-(2,5-dibromothiophen-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound BrC=1SC(=CC=1C=1NC=2C(=C3C=CC=NC3=C3N=CC=CC=23)N=1)Br ZPMYMUGEJTYYJI-UHFFFAOYSA-N 0.000 claims description 2
- PBQAEYDHXNDMEQ-UHFFFAOYSA-N 2-cyano-3-(8-hydroxyquinolin-5-yl)propanoic acid Chemical compound C(#N)C(C(=O)O)CC1=C2C=CC=NC2=C(C=C1)O PBQAEYDHXNDMEQ-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 claims description 2
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 claims description 2
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- 229920001651 Cyanoacrylate Polymers 0.000 abstract description 4
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical class C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 150000005041 phenanthrolines Chemical class 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 23
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- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物、制备方法和作染料敏化太阳能电池中染料敏化剂的应用。该染料分子结构是以苯并二噻吩衍生物(BDTT)或聚苯乙撑(PPV)作为电子给体(D),用过渡金属Cd(Ⅱ)与邻菲罗啉衍生物形成金属螯合物作为辅助电子受体单元(A)以增加了电荷的有效传输,碳碳双键作为π桥,氰基丙烯酸(CA)作为电子受体(A)和锚定基团。将电子给体和受体部分进行Yamamoto聚合反应,得到该类两种染料敏化剂PBDTT‑PhenCd和PPV‑PhenCd。本发明的优势在于该类染料在设计和合成上将无机、有机和高分子合理融为一体,光伏应用测试结果表明其具有较高的光伏性能:光电转化效率(η)达6.68%、低的成本和良好的光与热稳定性。
Description
技术领域
本发明涉及一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物及其制备方法和作为染料敏化太阳能电池中染料敏化剂的用途,属于功能材料中太阳能电池光电材料领域。
背景技术
染料敏化太阳能电池在和O’Regan在1991年研究发明以来不断取得进展,已经成为最具发展潜力的可再生与清洁能源的技术之一。染料敏化太阳能电池模仿光合作用原理,其中染料敏化剂(简称染料)承担着吸收太阳光以产生电子并传输电子的最重要功能,是影响染料敏化太阳能电池光伏性能的最关键的活性组成部分。染料敏化剂从分子结构上分为D-A型D-π-A型D-A’-π-A型,其中D-A’-π-A型染料是最新开发和最有发展潜力的结构类型,通过引入额外的辅助电子受体A,增强了染料的吸光响应,并使吸光范围向长波方向移动;辅助受体和主受体间的π桥在传递电子的同时,还能抑制电子复合以及暗电流的产生;所以D-A’-π-A型染料与其他类型相比,它具有更好的光、热稳定性和更高的光-电转换效率。总而言之,D-A’-π-A结构的染料有着明显的优势,如可以方便的调节染料能级,促进吸收带红移,并且电池的光伏性能明显得到改善,稳定性也有所提高。
本专利中邻菲罗啉并咪唑具有大的刚性结构,能与很多金属进行配位形成强的配位键而起拉电子作用,邻菲罗啉并咪唑衍生物合Cd(Ⅱ)配合物作为辅助电子受体,利于分子内电荷的转移,增大了染料的吸光程度;苯并二噻吩衍生物(BDTT)与苯乙撑(PV)是非常好的给体材料,而且形成的聚合金属配合物具有更大的π共轭结构,不仅有利于聚合金属配合物的空穴传输和电子传输,而且具有高的稳定性;Cd(Ⅱ)的辅助配体8-羟基喹啉衍生物作为π桥,氰基丙烯酸(CA)作为主电子受体(A)与锚定基团,有效的促进电子注入到TiO2导带,增加了电荷的有效传输,有助于提高染料光电效率。
通过以上设计,有助于得到光-电转换效率较高、稳定性好的新型染料,是染料敏化太阳能电池中是染料敏化剂发展的一个重要的新方向。本发明在获得一类含邻菲罗啉并咪唑衍生物合Cu(Ⅱ)聚合金属配合物的基础上合成了新的一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物。
发明内容
本发明的目的:在于提供一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物及其制备方法和在染料敏化太阳能电池中用作为染料敏化剂的应用。通过Yamamoto聚合在邻菲罗啉并咪唑衍生物的配体中引入苯并二噻吩衍生物(BDTT)或苯乙撑(PV)给体,合成两个具有D-A’-π-A结构的聚合金属配合物PBDTT-PhenCd和PPV-PhenCd,并应用于染料敏化太阳能电池中做染料敏化剂。
本发明的技术方案是:一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物,其特征在于,该化合物具有D-A’-π-A结构,其通式如式1:
一类具有含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物PBDTT-PhenCd和PPV-PhenCd的制备方法:
(1)2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉的制备:
将1,10-菲罗啉-5,6-二酮、2,5-二溴-3-噻吩甲醛与醋酸铵以1:1:20的比例加入到容器中,在N2保护下,用冰醋酸做为溶剂,升高温度溶解,直至120℃,搅拌回流5h,冷却至室温后,将混合液倒入冰水中,搅拌,用氨水调节pH=7,抽滤,洗涤,最后在无水CH3OH中重结晶,得到黄绿色产物2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉;
(2)2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f][1,10]菲罗啉的制备:
在容器中先后加入比例为1:1.4的2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉和NaH,在氮气保护下,加热至40℃,缓慢加入DMF溶液,1h后,再加入溴辛烷,加热至70℃,回流8-24h,冷却至室温,过滤,将滤液倒进蒸馏水,用CHCl3进行萃取,用无水MgSO4干燥,过滤后用减压蒸馏法除去溴辛烷后,并用5:5:1的石油醚,二氯甲烷和甲醇的混合液过柱纯化,得白色产物2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f][1,10]菲罗啉;
(3)镉金属配合物PhenCd的制备:
取比例为1:1的2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉与2-氰基-3-(8-羟基喹啉-5-基)丙酸于容器中,用四氢呋喃为溶剂,搅拌使其溶解。将醋酸镉在甲醇溶液溶解,逐滴加入到反应器中,加热,回流12h,冷却,过滤,并用无水CH3OH洗涤,干燥得到镉金属配合物PhenCd;
(4)聚合镉金属配合物PBDTT-PhenCd的合成制备:
取三苯基膦、锌粉、双三苯基膦氯化镍、联吡啶,2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩BDTT与镉金属配合物以2:50:10:1:10:10的比例加入到反应瓶中,然后加精制过的DMF,在氮气保护下,升温至90℃,反应48h,冷却,倒入过量的无水CH3CH2OH,静置过夜之后过滤,用无水CH3CH2OH进行多次洗涤,干燥得到以BDTT为给体含邻菲罗啉咪唑的D-A’-π-A型结构聚合镉金属配合PBDTT-PhenCd物染料敏化剂;
(5)聚合镉金属配合物PPV-PhenCd的合成制备:
取三苯基膦、锌粉、双三苯基膦氯化镍、联吡啶,1,4-二溴-2,5-二辛氧基苯PV与镉金属配合物以2:50:10:1:10:10的比例加入到反应瓶中,然后加精制过的DMF,在氮气保护下,升温至90℃,反应48h,冷却,倒入过量的无水CH3CH2OH,静置过夜之后过滤,用无水CH3CH2OH进行多次洗涤,干燥得到以PV为给体含邻菲罗啉咪唑的D-A’-π-A型结构聚合镉金属配合物PPV-PhenCd染料敏化剂。
一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物的用途:在染料敏化太阳能电池中用作染料敏化剂。
发明的主要优势在于:一类含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物,采用普通副族金属Cd(Ⅱ)与邻菲罗啉衍生物形成金属螯合物,有效的结合了有机染料和金属聚合物(MCP)材料的优点,将有机金属配合物聚合,扩大了配合物分子的大π体系,提高其载流子传输能力和稳定性,从而有助于提高光电转化效率;且用普通副族金属Cd(Ⅱ)代替贵金属钌合成聚合金属配合物染料,不仅能大大降低敏化太阳能电池成本而且能减少对环境的污染。
附图说明
图1本发明实施例合成的2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉的核磁氢谱(1HNMR)(400MHz,DMSO,TMS);
图2本发明实施例合成的2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f][1,10]菲罗啉的核磁氢谱(1HNMR)(400MHz,CDCl3,TMS);
图3本发明实施例合成的化合物PhenCd、PBDTT-PhenCd和PPV-PhenCd的红外光谱(IR)(KBr晶体压片,4000~400cm-1);
图4本发明实施例合成的化合物PBDTT-PhenCd和PPV-PhenCd的热重分析(TGA)曲线;
图5本发明实施例合成的化合物PBDTT-PhenCd和PPV-PhenCd的紫外-可见光(UV-vis)吸收光谱;
图6本发明实施例合成的化合物PBDTT-PhenCd和PPV-PhenCd的染料敏化太阳能电池电流密度-电压(J-V)曲线;
图7本发明实施例合成的化合物PBDTT-PhenCd和PPV-PhenCd的染料敏化太阳能电池外量子效率(IPCE)曲线。
具体实施方式
本发明的化合物的制备合成反应机理为:
下面结合具体实施例对本发明做进一步的说明。
实施例1:
一种含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物PBDTT-PhenCd。
一种以苯并二噻吩衍生物(BDTT)作为电子给体(D),邻菲罗啉并咪唑衍生物合Cd(Ⅱ)配合物为辅助电子接受体(A)、聚合度为x=8,y=8的D-A’-π-A型的聚合金属配合物PBDTT-PhenCd,其分子结构式如式2:
上述聚合金属配合物PBDTT-PhenCd的制备实施方法:
A.2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉的制备:分别称取1,10-菲罗啉-5,6-二酮0.3153g(1.5mol),2,5-二溴-3-噻吩甲醛0.4859g(1.5mol)以及醋酸铵2.3105g(30mol),加入到圆底烧瓶(单口,100ml),再加入冰醋酸(30ml),抽真空,充入N2气,升温至60℃时,固体全部溶解,再加热温度升至120℃,搅拌回流反应5h,冷却至室温后,将混合液倒入100ml冰的去离子水中,搅拌,变浑浊,缓慢滴加氨水直到pH为7,在此过程中逐渐出现黄色固体,然后抽滤,并用大量去离子水洗涤,最后在无水CH3OH中进行重结晶,得到晶型为雪花状的黄绿色产物0.4922g,产率:71%。1H-NMR(400MHz,DMSO,ppm):7.78(s,1H),7.82(q,2H),8.84(d,2H),9.13(d,2H).Anal.Calcd.for[C17H10N4Br2S]:C,44.18;H,2.18;S,6.94;Found:C,44.21;H,2.15;S,6.89.
B.2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f][1,10]菲罗啉的制备:称取2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f][1,10]菲罗啉0.4602g(1.0mmol)于100ml的三口瓶中,接着迅速加入0.0336g的NaH(1.4mmol),抽真空充氮气保护,温度升至40℃时,先将置于恒压滴液漏斗的17ml的DMF(干燥精制)缓慢滴加入反应体系,有气泡产生,约1h后不再产生气泡,体系颜色变为灰绿色,再慢慢滴加溴辛烷,滴完后,加热至70℃,回流12h,温度降低为室温后,过滤,将所得到的滤液倒入蒸馏水(约100ml)中,再用CHCl3进行萃取,干燥(无水MgSO4),然后过滤,旋除一部分溶剂,再进行减压蒸馏的操作,于120℃蒸去未反应的溴辛烷,并用体积比为5:5:1的石油醚,二氯甲烷和甲醇的混合液过柱纯化得白色产物0.4171g,产率为73%,1H-NMR(400MHz,CDCl3,ppm):13.72(s,1H),9.26(s,2H),9.09-9.11(d,H),8.64-8.66(d,1H),7.80(s,2H),7.28(s,1H),4.61(t,2H),1.27(m,10H),0.91(t,3H).Anal.Calcd.for[C25H24Br2N4S]:C,52.28;H,4.56;N,9.75,Br,27.82;S,5.58.Found:C,52.36;H,4.66;N,9.65,S,5.54.
C.镉配合物PhenCd的制备:称醋酸镉[Cd(CH3COO)2·2H2O]0.2932g(1.1mmol),溶解在20ml无水甲醇中备用。称取2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f][1,10]菲罗啉0.5724g(1.0mmol)和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸0.2402g(1.0mmol)于100ml的三口瓶中,再加入四氢呋喃25ml,搅拌,使固体溶解。将醋酸镉溶解在甲醇中,缓慢的逐滴加入,然后慢慢加热直到回流,继续反应12h。冷却,然后过滤除去滤液,用无水CH3OH反复进行洗涤,干燥,得到暗黄色固体PhenCd 0.7416g,产率:79%。FT-IR(KBr,4000~400cm-1):3426(-OH),2923(CH3),2854(CH2),2217(C≡N),1687(C=O),1121(C=N-M),506(N-M).Anal.Calcd for[C40H38Br2SN6O5Cd]:C,48.67%;H,3.88%;N,8.51%;S,3.26%.Found:C,48.61%;H,3.82%;N,8.59%,S,3.31%.
D.聚合镉金属配合物PBDTT-PhenCd的制备:分别称取配合物PhenCd 0.1848g(0.2mmol),2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩(BDTT)0.1474g(0.2mmol),三苯基膦(PPh3)0.1045g(0.4mmol),锌粉(Zn)0.0650g(1.0mmol),双三苯基膦氯化镍[Ni2(PPh3)Cl2]0.1312g(0.2mmol),联吡啶0.0031g(0.02mmol),加入到50ml的单口瓶中,再量取10ml精制过的DMF,加入上述烧瓶中。反应在氮气氛围中进行,将温度逐渐生至90℃,反应48h,冷却,然后将反应液倾倒至过量的无水CH3CH2OH,静置过夜之后过滤,滤渣用无水CH3CH2OH进行多次洗涤,干燥,产物为黄色固体,产率:64%,FT-IR(KBr,4000~400cm-1):3436(-OH),3031(Ar–H),2923(CH3),2854(CH2),2206(C≡N),1661(C=O),1564(C=C),1526(C=N),1105(C–O–M),493(N–M).Anal Calcdfor[C74H78N56S5O5Cd]:C,63.17%;H,5.91%;N,7.95%;S,11.41%.Found:C,63.13%;H,5.89%;N,5.89%;S,11.33%.n=7;PDI=2.28.
实施例2:
一种含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)的聚合金属配合物PPV-PhenCd。
一种以苯乙撑(PV)为电子给体(D),含邻菲罗啉并咪唑衍生物合Cd(Ⅱ)配合物为辅助电子接受体(A)、聚合度x=7,y=7的D-A-π-A型聚合金属配合物PPV-PhenCd,其分子结构式如式3:
上述聚合镉金属配合物PPV-PhenCd的制备方法:
A.与实施例1中步骤A的合成方法一致。
B.与实施例1中步骤B的合成方法一致。
C.与实施例1中步骤C的合成方法一致。
D.与实施例1中的步骤D类似,只是用1,4-二溴-2,5-二辛氧基苯(PPV)0.0985g(0.2mmol)来代替2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩(BDTT),获得产物为黄色固体产物PPV-PhenCd,产率:59%,FT-IR(KBr,4000~400cm-1):3428(-OH),3034(Ar–H),2924(CH3),2846(CH2),2207(C≡N),1665(C=O),1563(C=C),1520(C=N),1103(C–O–M),491(N–M).Anal Calcd for[C46H40N6SO5Cd]:C,61.03%;H,5.01%;N,9.25%;S,3.51%.Found:C,61.07%;H,4.97%;N,9.29%;S,3.61%.n=8;PDI=1.82.
实施例3:
分别测定聚合金属配合物PBDTT-PhenCd和PPV-PhenCd染料敏化剂的热失重曲线(TGA)。方法:Q50热重分析仪,N2保护下以25℃/min的升温速度进行测试,测试结果如图4。
实施例4:
以Computer-programmed Keithley 2611SourceMeter通过电脑控制测量,Solarsimulator(Oriel,91160-100091192,Perccell Technologies)为光源(500-W Xe,AM1.5G),电池活性电极有效面积为0.25cm2,分别测定以聚合金属配合物PBDTT-PhenCd和PPV-PhenCd为染料敏化剂的染料敏化太阳能电池的性能参数和光电转换效率,其电池电流密度-电压(J-V)曲线如图6,电池外量子效率(IPCE)曲线如图7。表一是它们的光伏性能和光电转换效率测试结果。
表一 聚合物染料敏化剂的光伏性能参数
Claims (3)
2.根据权利要求1所述的一类具有D-A’-π-A型结构的含邻菲罗啉并咪唑的聚合Cd(Ⅱ)金属配合物的制备方法:
(1)2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f] [1,10]菲罗啉的制备:
将1,10-菲罗啉-5,6-二酮、2,5-二溴-3-噻吩甲醛与醋酸铵以1:1:20的比例加入到容器中,在N2保护下,用冰醋酸做为溶剂,升高温度溶解,直至120℃,搅拌回流5 h,冷却至室温后,将混合液倒入冰水中,搅拌,用氨水调节pH=7,抽滤,洗涤,最后在无水CH3OH中重结晶,得到黄绿色产物2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f] [1,10]菲罗啉;
(2)2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f] [1,10]菲罗啉的制备:
在容器中先后加入比例为1:1.4的2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f] [1,10]菲罗啉和NaH,在氮气保护下,加热至40℃,缓慢加入DMF溶液,1 h后,再加入溴辛烷,加热至70℃,回流8-24 h,冷却至室温,过滤,将滤液倒进蒸馏水,用CHCl3进行萃取,用无水MgSO4干燥,过滤后用减压蒸馏法除去溴辛烷后,并用5:5:1的石油醚,二氯甲烷和甲醇的混合液过柱纯化,得白色产物2-(2,5-二溴噻吩-3-基)-1辛基-咪唑并[4,5-f] [1,10]菲罗啉;
(3)镉金属配合物PhenCd的制备:
取比例为1:1的2-(2,5-二溴噻吩-3-基)-1H-咪唑[4,5-f] [1,10]菲罗啉与2-氰基-3-(8-羟基喹啉-5-基)丙酸于容器中,用四氢呋喃为溶剂,搅拌使其溶解, 将醋酸镉在甲醇溶液溶解,逐滴加入到反应器中,加热,回流12 h,冷却,过滤,并用无水CH3OH洗涤,干燥得到镉金属配合物PhenCd;
(4)聚合镉金属配合物PBDTT-PhenCd的合成制备:
取三苯基膦、锌粉、双三苯基膦氯化镍、联吡啶,2,6-二溴-4,8-双[5-(2-乙基己基)噻吩-2-基]苯并[1,2-B:4,5-b]二噻吩BDTT与镉金属配合物以2:50:10:1:10:10的比例加入到反应瓶中,然后加精制过的DMF,在氮气保护下,升温至90℃,反应48 h,冷却,倒入过量的无水CH3CH2OH,静置过夜之后过滤,用无水CH3CH2OH进行多次洗涤,干燥得到以BDTT为给体含邻菲罗啉咪唑的D-A’-π-A型结构聚合镉金属配合物 PBDTT-PhenCd染料敏化剂;
(5)聚合镉金属配合物PPV-PhenCd的合成制备:
取三苯基膦、锌粉、双三苯基膦氯化镍、联吡啶,1,4-二溴-2,5-二辛氧基苯PV与镉金属配合物以2:50:10:1:10:10的比例加入到反应瓶中,然后加精制过的DMF,在氮气保护下,升温至90℃,反应48 h,冷却,倒入过量的无水CH3CH2OH,静置过夜之后过滤,用无水CH3CH2OH进行多次洗涤,干燥得到以PV为给体含邻菲罗啉咪唑的D-A’-π-A型结构聚合镉金属配合物PPV-PhenCd染料敏化剂。
3.根据权利要求1所述的一类具有D-A’-π-A型结构的含邻菲罗啉并咪唑的聚合Cd(Ⅱ)金属配合物的用途:在染料敏化太阳能电池中用作染料敏化剂。
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