CN102504210A - 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 - Google Patents
主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 Download PDFInfo
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- CN102504210A CN102504210A CN2011103190199A CN201110319019A CN102504210A CN 102504210 A CN102504210 A CN 102504210A CN 2011103190199 A CN2011103190199 A CN 2011103190199A CN 201110319019 A CN201110319019 A CN 201110319019A CN 102504210 A CN102504210 A CN 102504210A
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- aryl
- band gap
- narrow band
- alkyl
- conjugate polymer
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 6
- 150000004696 coordination complex Chemical class 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- -1 alkylthio-aryl Chemical group 0.000 claims description 19
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 8
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- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
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- 125000003545 alkoxy group Chemical group 0.000 claims description 4
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- 239000010948 rhodium Chemical group 0.000 claims description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- IDWJREBUVYSPKS-UHFFFAOYSA-N 3,8-dibromo-1,10-phenanthroline Chemical compound BrC1=CN=C2C3=NC=C(Br)C=C3C=CC2=C1 IDWJREBUVYSPKS-UHFFFAOYSA-N 0.000 description 1
- KZXODWQOXSIVDW-UHFFFAOYSA-N 3,8-dithiophen-2-yl-1,10-phenanthroline Chemical compound C1=CSC(C=2C=C3C(C4=NC=C(C=C4C=C3)C=3SC=CC=3)=NC=2)=C1 KZXODWQOXSIVDW-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 238000000835 electrochemical detection Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明涉及一种主链中含有金属配合物的有机共轭高分子,其结构如式Ⅰ所示,其中, M 代表过渡金属; 代表以 N 原子为配位原子的双齿配体, Ar 代表含氮和 / 或硫的芳杂环; X - 代表 Cl - 、 Br - 、 I - 、 PF 6 - 、 BF 4 - 、 CF 3 SO3 - ; n 为 10~100 的整数。本发明有机共轭高分子,具有更高的光电转化效率,当应用于有机太阳能电池器件中时更有利于光电能量转化效率的提升。本发明有机共轭高分子可通过 Suzuki 或者 Still 偶联反应制备,反应条件温和可控,制备方法简单高效,适于大规模生产。 Ⅰ 。
Description
技术领域
本发明属于有机光电材料领域,具体涉及一类主链中含有过渡金属配合物的窄带隙有机共轭高分子及其制备方法。
背景技术
有机聚合物太阳能电池由于质轻、易于加工、可大面积成膜、柔性、价格低廉及可实现卷对卷打印等优点,近十年来备受人们的关注而发展迅速。目前以窄带隙共轭高分子为主体材料的太阳能电池材料已经成为学术界和工业界的研究热点。一些大公司在有机薄膜太阳能电池的研发方面也取得了巨大的成功:美国的Solarmer Energy公司在2010年7月报道了光电转换效率为8.13%的有机聚合物薄膜太阳能电池器件;德国的Heliatek公司和美国的Konarka公司在2010年10月和11月分别报道了光电转换效率为8.3%的有机聚合物薄膜太阳能电池器件;最近日本的Mitsubishi Chemical公司报道了光电转换效率为9.2%的有机聚合物薄膜太阳能电池器件,已经十分接近有机太阳能电池工业化生产的效率门槛(10%的光电转换效率),有机太阳能电池的大规模应用指日可待(Service, R. F. Science 2011, 332, 293.)。
目前报道的光电转换效率最高的太阳能电池器件所用的材料还集中于含噻吩、噻吩衍生物及类噻吩类基团单元的窄带系有机共轭高分子上。而研究发现,过渡金属配位化合物在可见光区有强烈吸收,因此可以预测,如果能够在有机太阳能电池器件中利用过渡金属对于提高太阳能电池的光电转化效率将有很大的帮助。
发明内容
本发明的目的是克服现有技术的不足,提供一种主链中含有过渡金属配合物的窄带隙有机共轭高分子,其具有更高的光电转化效率。
本发明的另一目的是提供上述主链中含有过渡金属配合物的窄带隙有机共轭高分子的制备方法。
本发明的第三个目的是将这种主链中含有过渡金属配合物的窄带隙有机共轭高分子应用到有机太阳能电池器件中。
为实现上述目的,本发明采取如下技术方案:
一种主链中含有过渡金属配合物的窄带隙有机共轭高分子,结构如式Ⅰ所示:
Ⅰ
其中,M代表过渡金属;代表以N原子为配位原子的双齿配体;Ar代表含氮和/或硫的芳杂环;X
-
代表Cl
-
、Br
-
、I
-
、PF
6
-
、BF
4
-
、CF
3
SO
3
-
;n为10~100的整数。
根据本发明,M为钌、铑或铼。
优选地,:为以下结构:
(1);(2);(3);(4);(5);(6);
(7);(8);
其中,R为氢原子、卤素原子、烷基、烷氧基、烷硫基、烷基氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基乙炔基或者氰基。
进一步地,为以下结构:
(1);(3)。
优选地,Ar为以下结构:
(9);(10);(11);(12);(13);(14);(15);(16);(17);(18);(19);(20);(21);(22);(23);(24);(25);(26);(27);(28);(29);(30);(31);(32);(33);(34);(35);(36);(37);(38);(39);(40);(41);(42);(43);(44);
其中,R
1
为卤素原子、烷基、烷氧基、烷硫基、基烷氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基炔基或氰基。
进一步地,Ar为以下结构:
(31);(34)。
本发明含有过渡金属配合物的窄带隙有机共轭高分子,可以在Pd催化剂存在下,由含有两个氯、两个溴或两个碘的卤素基团的过渡金属配合物单体单元与含有两个硼酸基、硼酸酯基或者烷基锡基的芳杂环Ar单体单元通过Suzuki偶联反应或是Still偶联反应制备而得(Yin; Liebscher, J. Chemical Reviews 2006, 107, 133-173.),且卤素基团优选为溴。
具体的反应方程式可用式Ⅱ表示:
Ⅱ。
上述的有机共轭高分子可应用于有机太阳能电池器件中。
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:
本发明主链中含有过渡金属配合物的窄带隙有机共轭高分子,具有更高的光电转化效率,当应用于有机太阳能电池器件中时更有利于光电能量转化效率的提升;
本发明窄带隙有机共轭高分子通过Suzuki或者Still偶联反应制备,反应条件温和可控,制备方法简单高效,适于大规模生产。
附图说明
图1是实施例3中所制得的高分子polymer 1在CHCl
3
溶液中的UV—vis吸收光谱图。
具体实施方式
下面结合具体的实施例对本发明做进一步详细的说明,但不限于这些实施例。
实施例1
配体3,8-二(2-溴噻吩)菲啰啉(化合物4)的合成,包括以下两步:
(1)、将5.00g 3,8-二溴菲啰啉(化合物1),4.16g 2-硼酸噻吩(化合物2),10.22g K
2
CO
3
,6.00g Bu
4
NBr(四丁基溴化铵)加入500.0mL三口烧瓶中,再加入100.0mL Toluene(甲苯),75.0mL Ethanol(乙醇),50.0mL H
2
O,然后再向烧瓶中充N
2
10min,再向烧瓶中加入1.71g Pd(PPh
3
)
4
[四(三苯基膦)钯],用N
2
将烧瓶中的气体置换三次,最后在N
2
保护下加热至90℃搅拌反应59h。反应结束后旋转蒸发除去溶剂,再用CH
2
Cl
2
/H
2
O萃洗,浓缩有机相,然后以Al
2
O
3
为固定相,CH
2
Cl
2
/Et
3
N(三乙基胺)= 50:1为流动相过柱分离提纯,得3,8-二噻吩基菲啰啉(化合物3)2.37g;
(2)、将1.40g步骤(1)制备所得的3,8-二噻吩基菲啰啉(化合物3)溶于20mL DMF和10mL CHCl
3
的混合溶剂中,然后在避光下向其中加入1.52g NBS(N-溴代丁二酰亚胺)的10mL DMF溶液,再在氩气保护下于50℃反应5h,反应结束后冷却至0℃后过滤,所得固体用水充分淋洗后干燥,得黄色固体产物1.84g[即化合物4,配体3,8-二(2-溴噻吩)菲啰啉],收率:90.0%。化合物4的表征条件及结果如下:1H NMR (D6-DMSO,400MHz),δ(ppm): 9.36(d, J=2.0Hz, 2H), 8.61(d, J=2.0Hz, 2H), 7.99(s, 2H), 7.72(d, J=4.0Hz, 2H), 7.39(d, J=4.0Hz, 2H)。
具体合成路线如下:
实施例2
含过渡金属钌的配合物单体7的合成:
将656.6mg化合物5,350.0mg化合物4加入100mL单口烧瓶中,再加入15.0mL HOCH
2
CH
2
OH,然后在N
2
保护下升温搅拌回流反应2h。反应结束后将反应液滴加到1.2g NH
4
PF
6
的15.0mL水溶液中(将化合物6转变为化合物7),有大量红色絮状沉淀生成,离心分离得深红色固体1.02g,再将所得深红色固体以CH
2
Cl
2
/CH
3
CH
2
OH =30:1为流动相,过硅胶柱分离提纯,得深红色固体化合物7 纯品520.0mg,收率:45.8%。化合物7的表征条件及结果如下:1H NMR (D6-DMSO,400MHz),δ(ppm): 9.02(d, J=2.0Hz, 2H), 8.84(s, 2H), 8.73(s, 2H), 8.31(s, 2H), 7.890(d, J=2.0Hz, 2H), 7.75(d, J=5.6Hz, 2H), 7.65(d, J=5.6Hz, 2H), 7.53(m, 2H), 7.46(d, J=4.0Hz, 2H), 7.38(d, J=4.0Hz, 2H), 7.22(m, 2H), 2.87(t, 4H), 2.72(t, 4H), 1.76(t, 4H), 1.62(t, 4H), 1.37-1.19(m, 48H), 0.82(m, 12H)。
具体合成路线如下:
实施例3
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer 1的合成:
将257.0mg 单体7,116.0mg 化合物8,8.0mg Pd(PPh
3
)
4
加入100mL三口烧瓶中,然后在N
2
保护下将3.0mL 无水DMF(N,N-二甲基甲酰胺)、5.0mL 无水甲苯加入烧瓶中,N
2
保护下升温搅拌回流反应40h。反应结束后将反应液滴加入约300mL CH
3
OH中,有大量固体析出,减压抽滤得红色固体,先将红色固体用硅藻土简单过滤以除去金属催化剂,然后再将红色固体放入索氏提取器中依次用正己烷、CH
3
OH、CHCl
3
为萃洗剂充分萃洗,最后取CHCl
3
萃洗液旋蒸除去溶剂得红色固体Polymer 1约130mg。GPC:Mw(23×10
3
g/mmol),PDI(1.18)。
具体合成路线如下:
实施例4
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer 2的合成:
将257.0mg 单体7,98.8mg 化合物9,8.0mg Pd(PPh
3
)
4
加入100mL三口烧瓶中,然后在N
2
保护下将3.0mL 无水DMF(N,N-二甲基甲酰胺),5.0mL 无水甲苯加入烧瓶中,N
2
保护下升温搅拌回流反应45h。反应结束后将反应液滴加入约300mL CH
3
OH中,有大量固体析出,减压抽滤,先将所得固体用硅藻土简单过滤以除去金属催化剂,然后再将固体放入索氏提取器中依次用正己烷、CH
3
OH、丙酮、四氢呋喃、CHCl
3
为萃洗剂充分萃洗,最后取CHCl
3
萃洗液旋蒸除去溶剂得固体产物Polymer 2约210mg。GPC:Mw(56×10
3
g/mmol),PDI(1.20)。
具体合成路线如下:
实施例5
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer 3的合成:
将257.0mg 单体7,143.0mg 化合物10,8.0mg Pd(PPh
3
)
4
加入100mL三口烧瓶中,然后在N
2
保护下将3.0mL 无水DMF(N,N-二甲基甲酰胺),5.0mL 无水甲苯加入烧瓶中,N
2
保护下升温搅拌回流反应40h。反应结束后将反应液滴加入约300mL CH
3
OH中,有大量固体析出,减压抽滤,先将所得固体用硅藻土简单过滤以除去金属催化剂,然后再将固体放入索氏提取器中依次用正己烷、CH
3
OH、丙酮、四氢呋喃、CHCl
3
为萃洗剂充分萃洗,最后取CHCl
3
萃洗液旋蒸除去溶剂得固体产物Polymer 3约230mg。GPC:Mw(36×10
3
g/mmol),PDI(1.32)。
实施例6
对窄带隙有机共轭高分子Polymer 1的电化学及光学性质进行测验:
电化学检测:
Polymer 1 的电化学性质是通过粘附在铂电极上的Polymer 1的薄膜在无水无氧条件下经循环伏安法测定的,氧化起始电位Eox = 0.78V, 还原起始电位E
red
= -1.15V, 用二茂铁作基准物,将E
ox
、E
red
带入公式E
HOMO
= - (E
ox
+ 4.80)(eV), E
LUMO
= - (E
red
+ 4.80)(eV)得到Polymer 1的E
HOMO
= 5.58 eV,E
LUMO
= -3.65 eV, Eg = 1.93 eV。
光学检测:
对Polymer 1的光谱性质进行检测,其UV—vis吸收光谱如图1所示。
由窄带隙有机共轭高分子Polymer 1的HOMO—LUMO能级和UV—vis吸收光谱可知Polymer 1在有机光伏领域有很好的应用前景。
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (10)
2.根据权利要求1所述的窄带隙有机共轭高分子,其特征在于:M为钌、铑或铼。
5.根据权利要求1所述的窄带隙有机共轭高分子,其特征在于:Ar为以下结构:
(9);(10);(11);(12);(13);(14);(15);(16);(17);(18);(19);(20);(21);(22);(23);(24);(25);(26);(27);(28);(29);(30);(31);(32);(33);(34);(35);(36);(37);(38);(39);(40);(41);(42);(43);(44);
其中,R1为卤素原子、烷基、烷氧基、烷硫基、基烷氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基炔基或氰基。
8.权利要求1~7中任一项所述的窄带隙有机共轭高分子的制备方法,其特征在于:所述有窄带隙机共轭高分子通过Suzuki偶联反应或者Still偶联反应制备而成。
10.权利要求1~7中任一项所述的窄带隙有机共轭高分子在有机太阳能电池器件中的应用。
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CN103881060A (zh) * | 2012-12-24 | 2014-06-25 | 海洋王照明科技股份有限公司 | 一种萘并二噻吩基共聚物及其制备方法与聚合物太阳能电池 |
CN108033982A (zh) * | 2017-12-25 | 2018-05-15 | 长春理工大学 | 一种聚集诱导磷光增强Re(I)配合物及其制备方法 |
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