CN111217840B - 一种线性邻菲咯啉铜配合物及其制备方法与应用 - Google Patents
一种线性邻菲咯啉铜配合物及其制备方法与应用 Download PDFInfo
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- -1 phenanthroline copper complex Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000004699 copper complex Chemical class 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 6
- 150000005045 1,10-phenanthrolines Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006303 photolysis reaction Methods 0.000 abstract description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 5
- 239000003480 eluent Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- HTGPMSIMSVMJKL-UHFFFAOYSA-N 3,8-bis(2-methoxyphenyl)-1,10-phenanthroline Chemical compound COC1=C(C=CC=C1)C=1C=NC2=C3N=CC(=CC3=CC=C2C1)C1=C(C=CC=C1)OC HTGPMSIMSVMJKL-UHFFFAOYSA-N 0.000 description 1
- UPVLROTVOMEKOV-UHFFFAOYSA-N 3,8-bis(3,4,5-trimethoxyphenyl)-1,10-phenanthroline Chemical compound COC=1C=C(C=C(C=1OC)OC)C=1C=NC2=C3N=CC(=CC3=CC=C2C=1)C1=CC(=C(C(=C1)OC)OC)OC UPVLROTVOMEKOV-UHFFFAOYSA-N 0.000 description 1
- CATCLWANNMMVJF-UHFFFAOYSA-N 3,8-bis(3,5-dimethylphenyl)-1,10-phenanthroline Chemical compound CC=1C=C(C=C(C=1)C)C=1C=NC2=C3N=CC(=CC3=CC=C2C=1)C1=CC(=CC(=C1)C)C CATCLWANNMMVJF-UHFFFAOYSA-N 0.000 description 1
- XSLKUWOISFOCKV-UHFFFAOYSA-N 3,8-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CN=C2C3=NC=C(C=4C=CC=CC=4)C=C3C=CC2=C1 XSLKUWOISFOCKV-UHFFFAOYSA-N 0.000 description 1
- UXRZLDREKITWRO-UHFFFAOYSA-N P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 Chemical compound P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 UXRZLDREKITWRO-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
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Abstract
本发明涉及一种线性邻菲咯啉铜配合物及其制备方法,以及其作为光敏材料在光解水制氢领域的应用。本发明方法制备得到的线性邻菲咯啉铜配合物是将3,8位和2,9位修饰后的1,10‑邻菲咯啉与Cu(I)和磷配体配位形成的铜基光敏剂,其制备方法为:在惰性气体保护下,将3,8位和2,9位修饰后的1,10‑邻菲咯啉配体、磷配体与一价铜盐溶于有机溶剂中,在一定温度下反应一段时间,反应结束后对反应液减压脱溶,经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到得到金属铜配合物。所述铜配合物可应用于光解水制氢、光电材料等领域。
Description
技术领域
本发明涉及一种线性邻菲咯啉铜配合物及其制备方法,以及其作为光敏材料在光解水制氢领域的应用。
背景技术
作为廉价金属的一价铜配合物由于在催化、光电材料、生物探针和太阳能电池等领域中的应用而受到国内外专家的广泛关注。含有菲咯啉的铜基光敏剂是由经1,10-邻菲咯啉分别在4,7位和2,9位修饰后作为氮配体与Cu(I)和磷配体配位形成的。
通过修饰可以增强配合物荧光强度,使其具有良好的发光性能和光学活性。S.Y.Park等报道了一种在菲咯啉4,7位用三芳胺修饰后的铜配合物,经过修饰后,改变了配合物的电子云分布,抑制了空间构型的扭曲,从而提高了制氢活性。本发明旨在通过对1,10-邻菲咯啉3,8位及2,9位的修饰,增强配合物的荧光强度、活性和刚性,使其具有良好的制氢效果和物理化学性能。
发明内容
本发明的目的在于解决现有技术问题的不足,提供一种在3,8位和2,9位修饰后的1,10-邻菲咯啉与Cu(I)和磷配体配位形成的铜基氮磷杂配光敏剂,且这种菲咯啉铜配合物呈线性结构,与文献报道的菲咯啉(非线性)铜基光敏剂有所不同,同时提供其制备方法和光电物理表征,以及其在光解水制氢气中的应用。
为了实现上述发明目的,本发明提供以下技术方案:
一种线性邻菲咯啉铜配合物,其分子结构为轴对称结构,如式(I)所示:
式(I)中,
R1为氢或C1-C12烷氧基;R2为氢、C1-C12烷基或C1-C12烷氧基;R3为氢或C1-C12烷基;
X-为六氟磷酸根、四氟硼酸根、氯离子、溴离子或碘离子。
更优选的,本发明所述的一种线性邻菲咯啉铜配合物,R1为甲氧基,R2为氢,R3为异丙基,X为六氟磷酸根,其分子结构如式(II)所示。
本发明还提供了一种所述线性邻菲咯啉铜配合物的制备方法,所述的制备方法为:惰性气体保护下,将3,8位和2,9位修饰后的1,10-邻菲咯啉配体、磷配体与一价铜盐溶于有机溶剂中,在一定温度下反应一定时间,反应结束后对反应液减压脱溶,经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到金属铜配合物。
优选的,所述3,8位和2,9位修饰后的1,10-邻菲咯啉配体为式(III)所示的邻菲咯啉配体。
优选的,所述一价铜盐为六氟磷酸四乙腈合铜、四氟硼酸亚铜、六氟磷酸亚铜、氯化亚铜、溴化亚铜或碘化亚铜。
优选的,所述磷配体为Xantphos、PPh3、Ph2PCH2CH2PPh2、(Ph2PCH2CH2)2PPh、(Ph2PCH2CH2)3P或4,5-双二苯基磷-9,9-二甲基氧杂蒽。
优选的,所述邻菲咯啉配体、磷配体与一价铜盐的物质的量之比为1:(0.5~2):(0.5~5),优选1:1:1。
优选的,所述有机溶剂为甲醇、乙醇、异丙醇、丁醇、丙酮、四氢呋喃、乙酸乙酯、甲苯、二氯甲烷或氯仿,所述有机溶剂的体积用量以邻菲咯啉配体的质量计为1~500mL/g。
优选的,所述反应温度为-20~100℃,更优选为25℃。
优选的,所述反应时间为1~72小时,更优选为3小时。
所述的线性邻菲咯啉铜配合物作为光敏材料的应用:本发明方法制备得到的线性邻菲咯啉铜配合物可作为光敏剂,与光催化剂例如PdCl2、Fe3(CO)12等一起使用于光催化反应中。
本发明与现有技术相比,其有益效果主要体现在:提供了一种新型的线性邻菲咯啉铜配合物,所述铜配合物是通过邻菲咯啉配体与含氮含磷的其他配体以及一价铜盐作用得到的铜基光敏剂,可应用于光解水制氢、光电材料等领域。
附图说明
图1是CuPS1-4的紫外吸收(左边线条)和荧光发射光谱(右边线条);
图2是CuPS1-4光敏剂在THF中的发光寿命结果。
具体实施方式
下面结合附图,并通过具体实施例对本发明的技术方案作进一步的具体说明。
实施例1 3,8-二(苯基)-1,10-菲咯啉铜(I)络合物的制备
氮气保护下,将氮配体3,8-二(苯基)-1,10-菲咯啉(1mmol)、磷配体4,5-双(二苯基膦)-9,9-二甲基氧杂蒽(1mmol)和六氟磷酸四乙腈铜(1mmol)溶于10mL二氯甲烷,25℃下反应3小时后浓缩经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到1.083g产物,收率90%,ESI-MS(+):1057.4。
实施例2 3,8-二(甲氧苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物的制备
氮气保护下,将氮配体3,8-二(甲氧苯基)-1,10-菲咯啉(1mmol)、磷配体PPh3(1.5mmol)和四氟硼酸亚铜(1.5mmol)溶于50mL四氢呋喃,10℃下反应24小时后浓缩经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到1.162g产物,收率92%,ESI-MS(+):1117.4。
实施例3 3,8-二(3,5-二(甲基)苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物的制备
氩气保护下,将氮配体3,8-二(3,5-二(甲基)苯基)-1,10-菲咯啉(1mmol)、磷配体4,5-双二苯基磷-9,9-二甲基氧杂蒽(0.5mmol)和六氟磷酸亚铜(0.5mmol)溶于1mL甲苯,100℃下反应1小时后浓缩经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到1.197g产物,收率95%,ESI-MS(+):1113.4。
实施例4 3,8-二(3,4,5-三(甲氧基)苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物
氮气保护下,将氮配体3,8-二(3,4,5-三(甲氧基)苯基)-1,10-菲咯啉(1mmol)、磷配体Xantphos(2mmol)和六氟磷酸四乙腈铜(5mmol)溶于150mL甲醇,-20℃下反应72小时后浓缩经硅胶柱层析分离,收集含目标化合物的洗脱液,浓缩干燥得到1.261g产物,收率94%,ESI-MS(+):1237.4。
实施例5实施例1的3,8-二(苯基)-1,10-菲咯啉铜(I)络合物在太阳能光解水中的应用
在无氧容器中,加入实施例1制得的3,8-二(苯基)-1,10-菲咯啉铜(I)络合物(4.20mg,3.5μmol),催化剂Fe3(CO)12(2.5mg,5μmol),THF/Et3N/H2O(4:3:1,体积比)混合溶剂10mL,300W氙灯照射15小时,获得12.8mL氢气。
实施例6实施例2的3,8-二(甲氧苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物在太阳能光解水中的应用
在无氧容器中,加入实施例2制得的3,8-二(甲氧苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物(4.42mg,3.5μmol),催化剂Fe3(CO)12(2.5mg,5μmol),THF/Et3N/H2O(4:3:1,体积比)混合溶剂10mL,300W氙灯照射18小时,获得24.1mL氢气。
实施例7实施例3的3,8-二(3,5-二(甲基)苯基)-2,9-二异丙基)-1,10-菲咯啉铜(I)络合物在太阳能光解水中的应用
在无氧容器中,加入实施例3制得的3,8-二(3,5-二(甲基)苯基)-2,9-二(异丙基)-1,10-菲咯啉铜(I)络合物(4.40mg,3.5μmol),催化剂Fe3(CO)12(2.5mg,5μmol),THF/Et3N/H2O(4:3:1,体积比)混合溶剂10mL,300W氙灯照射15小时,获得18.6mL氢气。
实施例8实施例4的3,8-二(3,4,5-三(甲氧基)苯基)-2,9-二异丙基)-1,10-菲咯啉铜(I)络合物在太阳能光解水中的应用
在无氧容器中,加入实施例3制得的3,8-二(3,4,5-三(甲氧基)苯基)-2,9-二异丙基)-1,10-菲咯啉铜(I)络合物(4.46mg,3.5μmol),催化剂Fe3(CO)12(2.5mg,5μmol),THF/Et3N/H2O(4:3:1,体积比)混合溶剂10mL,300W氙灯照射20小时,获得35mL氢气。
实施例9铜基光敏剂的光电物理性能:紫外吸收、荧光发射强度测试
将上述4个实施例得到的铜配合物CuPS1(实施例1),CuPS2(实施例2),CuPS3(实施例3),CuPS4(实施例4)配成浓度为1×10-5M的溶液,溶剂为四氢呋喃,分别进行紫外吸收和荧光发射强度测试,测试结果见附图1。之后又进行了淬灭实验和Stern-Volmer方程计算,发现制氢是一个还原淬灭的过程。
实施例10铜基光敏剂的荧光寿命测试
分别将3.5μmol上述4个实施例制得的铜配合物溶解在50mL四氢呋喃中,进行荧光寿命的测试,测试结果为:(a)CuPS1,201ns;(b)CuPS2,209ns;(c)CuPS3,186ns;(d)CuPS4,221ns。其中CuPS4的寿命长达221ns,说明CuPS4具有极好的制氢效果。
以上所述的实施例只是本发明的较佳方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (8)
3.一种权利要求1所述线性邻菲咯啉铜配合物的制备方法,其特征在于,所述的制备方法为:惰性气体保护下,将3,8位和2,9位修饰后的1,10-邻菲咯啉配体、磷配体与一价铜盐溶于有机溶剂中,在一定温度下反应一定时间,反应结束后对反应液减压脱溶,经硅胶柱层析分离后浓缩干燥得到金属铜配合物;所述一价铜盐为六氟磷酸四乙腈合铜、四氟硼酸亚铜、六氟磷酸亚铜、氯化亚铜、溴化亚铜或碘化亚铜;所述磷配体为Xantphos、PPh3、Ph2PCH2CH2PPh2、 (Ph2PCH2CH2)2PPh、 (Ph2PCH2CH2)3P或4,5-双二苯基磷-9,9-二甲基氧杂蒽。
4.根据权利要求3所述一种线性邻菲咯啉铜配合物的制备方法,其特征在于,所述邻菲咯啉配体、磷配体与一价铜盐的物质的量之比为1:(0.5~2):(0.5~5)。
5.根据权利要求3所述一种线性邻菲咯啉铜配合物的制备方法,其特征在于,所述有机溶剂为甲醇、乙醇、异丙醇、丁醇、丙酮、四氢呋喃、乙酸乙酯、甲苯、二氯甲烷或氯仿,所述有机溶剂的体积用量以邻菲咯啉配体的质量计为1~500mL/g。
6.根据权利要求3所述一种线性邻菲咯啉铜配合物的制备方法,其特征在于,所述反应温度为-20~100℃,反应时间为1~72小时。
7.根据权利要求3所述一种线性邻菲咯啉铜配合物的制备方法,其特征在于,所述邻菲咯啉配体、磷配体与一价铜盐的物质的量之比为1:1:1,所述反应温度为25℃,反应时间为3小时。
8.如权利要求1所述的线性邻菲咯啉铜配合物作为光敏材料的应用。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004059552A (ja) * | 2002-07-31 | 2004-02-26 | Japan Science & Technology Corp | 有機金属錯体およびその製造方法ならびにそれを用いた電荷保持材料および単電子トランジスター |
CN104892598A (zh) * | 2015-05-19 | 2015-09-09 | 南京信息工程大学 | 一种1,10-菲啰啉衍生物及其制备方法与应用 |
CN108250224A (zh) * | 2018-03-09 | 2018-07-06 | 南京邮电大学 | 一种Cu(I)配合物的寿命调控方法及其应用 |
CN111100124A (zh) * | 2019-11-27 | 2020-05-05 | 浙江工业大学 | 一种线性邻菲咯啉化合物及其制备方法和应用 |
-
2020
- 2020-01-17 CN CN202010054171.8A patent/CN111217840B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004059552A (ja) * | 2002-07-31 | 2004-02-26 | Japan Science & Technology Corp | 有機金属錯体およびその製造方法ならびにそれを用いた電荷保持材料および単電子トランジスター |
CN104892598A (zh) * | 2015-05-19 | 2015-09-09 | 南京信息工程大学 | 一种1,10-菲啰啉衍生物及其制备方法与应用 |
CN108250224A (zh) * | 2018-03-09 | 2018-07-06 | 南京邮电大学 | 一种Cu(I)配合物的寿命调控方法及其应用 |
CN111100124A (zh) * | 2019-11-27 | 2020-05-05 | 浙江工业大学 | 一种线性邻菲咯啉化合物及其制备方法和应用 |
Non-Patent Citations (5)
Title |
---|
1,10-菲咯啉衍生物的设计合成及其应用研究;黄道臣;《全国优秀硕士论文全文数据库》;20160615(第06期) * |
1,10-菲咯啉衍生物的设计合成及其铜络合物性能研究;邹亮;《全国优秀硕士论文全文数据库》;20190415(第04期) * |
Heteroleptic copper(I) photosensitizers with carbazole-substituted phenanthroline ligands: Synthesis, photophysical properties and application to photocatalytic H2 generation;Zhe-Jian Yu et al;《Dyes and Pigments》;20181111;第162卷;771-775 * |
Photocatalytic Water Reduction with Copper-Based Photosensitizers: A Noble-Metal-Free System;Shu-Ping Luo et al;《Angew. Chem. Int. Ed.》;20121009;第52卷;419-423 * |
Selective and efficient synthesis of di-, tri-and tetrasubstituted 1, 10-phenanthrolines;Christiane Dietrich-Buchecker et al;《Tetrahedron Letters》;19991231;第40卷;3395-3396 * |
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