CN100415715C - 紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物、合成方法及用途 - Google Patents
紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物、合成方法及用途 Download PDFInfo
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- -1 Super-phthalocyanine compound Chemical class 0.000 title abstract description 24
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 title abstract description 8
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 title abstract 3
- 241000206607 Porphyra umbilicalis Species 0.000 title abstract 3
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 claims description 55
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
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- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 claims 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 48
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- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 27
- 125000004429 atom Chemical group 0.000 description 13
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- RZZZFXPOFKWSOB-UHFFFAOYSA-N superphthalocyanine Chemical compound C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=NC2=NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 RZZZFXPOFKWSOB-UHFFFAOYSA-N 0.000 description 2
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- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
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Abstract
本发明公开一类紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物、合成方法及用途，具有全新的酞菁类化合物的基本结构，表现出一系列已有的酞菁类化合物所不具备的新的性质。这些性质是：UV-VIS-NIR吸收光谱具有三个强吸收峰，其中最有特征的是1428nm处时附近出现的近红外吸收；表面光伏特性；光致发光特性；电致发光特性；超高的热稳定性；良好的导电性等。这类分子所具有的一系列独特的性质，使得该类化合物在众多重要领域中具有重要的作用。这项工作将酞菁类化合物分子中紫菜嗪环的基本结构从三种增加到四种，为酞菁类化合物家族增添了一个新族。
Description
技术领域：
本发明涉及一类紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物、合成方法及用途，属于酞菁类化合物的合成方法及相关材料制备的技术领域。
背景技术：
酞菁类化合物是一类应用广泛，非常重要的功能分子。目前，酞菁类化合物的应用领域已涉及到化学传感器件、电子照相材料、半导体器件、有机导电材料、癌症的光动力治疗、太阳能电池材料、液晶显示材料、非线性光学材料、激光染料、燃料电池、光信息存储等领域。酞菁自1907年第一次由布鲁恩(Braun)等人合成后，已形成拥有巨大数目衍生物的家族。在这酞菁化合物家族中，按酞菁分子中紫菜嗪环含有的异吲哚单元数分类，具有四个异吲哚单元的酞菁族、具有五个异吲哚单元的超酞菁族和具有三个异吲哚单元的亚酞菁族。除具有五个异吲哚单元的超酞菁族化合物，由于稳定性较差、化合物数目较少以外，具有四个异吲哚单元的酞菁族和具有三个异吲哚单元的亚酞菁族都有数目众多的衍生物。紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物未见报道。
发明内容：
本发明提供一类紫菜嗪环中具有六个异吲哚结构亚单元的超酞菁类化合物、合成方法及用途，为酞菁类化合物家族中增添了新的一族和为众多领域提供新的材料。
下述通式(1)化合物，具有以下结构：
通式(1)化合物中，M包括下表所列元素的原子：
| H | ||||||||||||||
| Li | ||||||||||||||
| Na | Mg | Al | Si | P | ||||||||||
| K | Ca | Sc | Ti | V | Cr | Mn | Fe | Co | Ni | Cu | Zn | Ga | Ge | As |
| Y | Zr | Nb | Mo | Tc | Ru | Rh | Pd | Ag | Cd | In | Sn | Sb | ||
| Ba | La | Hf | Ta | W | Re | Os | Ir | Pt | Au | Hg | T1 | Pb | ||
| Ac | ||||||||||||||
| Ce | Pr | Nd | Pm | Sm | Eu | Gd | Tb | Dy | Ho | Er | Tm | Yb | Lu | |
| Th | Pa | U | Np | Pu | Am |
A1、A2、A3、A4为元素C、N原子；R1、R2、R3、R4为氢及各种卤原子如氟、氯、溴、碘；或硝基、磺酸基、带脂肪烃基取代的磺酸基；带有芳基取代的苯环上连有氟、氯、溴、碘、硝基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代的磺酸基；羰基、烷氧羰基及芳氧基为苯环上连有氟、氯、溴、碘、硝基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代苯基的芳氧基羰基；羟基及烷氧基；芳氧基为苯环上连有氟、氯、溴、碘、硝基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代苯基的芳氧基；氨基、带脂肪烃基取代的胺基、带有芳基取代的苯环上连有氟、氯、溴、碘、硝基、磺酸基、氨基、羟基、羰基、及各种烷氧基的取代的胺基；R5、R6为具有下面结构的基团：
通式(1)中I，II，III部分可以是相同结构，也可以是不同结构。
下述通式(2)化合物，具有以下结构：
通式(2)化合物中，M1、M2与通式(1)M所代表的元素的原子范围相同，M1和M2可以是同一种元素的原子，也可以是不同种元素的原子；通式(2)中A1、A2、A3、A4、A1`、A2`、A3`、A4`、R1、R2、R3、R4、R1`、R2`、R3`、R4`与通式(1)A1、A2、A3、A4所代表的元素原子的范围和R1、R2、R3、R4所代表的元素原子及基团的范围相同；
通式(2)中I、II、III、IV、V、VI部分可以是相同结构，也可以是不同结构。
通式(1)化合物的制备方法：
通式(1)化合物可从用通式(3)化合物来合成，通式(3)化合物中A1、A2、A3、A4的原子和R1、R2、R3、R4取代基与通式(1)化合物中A1、A2、A3、A4所代表的元素原子的范围和R1、R2、R3、R4所代表的原子及基团的范围相同；R代表羧基、氰基；R`…R`代表羧酸酐基、羧酸亚胺基、1，3-异吲哚基；
合成包括以下步骤：
反应所用的溶剂包括喹啉、硝基苯、三氯苯、1-氯萘、异戊醇、尿素；
向某种如上提到的单一或混合溶剂中加入一定量的通式(3)化合物与通式(1)化合物中M所代表的元素的单质及化合物，按摩尔比：通式(3)化合物/M＝1.5～5.5/1相混合的原料，加入一定量的催化剂后，装入密闭的容器，在180～240℃条件下反应8至48小时，得到黑色固体，在10-4～10-10Pa，200～300℃条件下去除杂质后得到通式(2)化合物；
所述的单质和化合物包括卤化盐(CuCl)、硫酸盐(NiSO4)、醋酸盐(HfAc2)、硝酸盐(AgNO3)；
所述的催化剂包括钼酸铵、醇钠。
通式(2)化合物的制备方法，包括以下步骤：
通式(2)化合物可用通式(1)化合物制备，将通式(1)化合物装入一个带有真空和可以加的热反应装置中，在10-4～10-10Pa，400～600℃条件下反应8～48小时，发生双分子缩合后得到通式(2)化合物。
以通式(1)化合物做为合成酞菁化合物的中间体化合物，与另一合成酞菁的原料化合物按一定比例混合，在一定条件下可合成出紫菜嗪环中含有三个、四个、五个及六个异吲哚结构亚单元的酞菁化合物。
本发明所提供的通式(2)化合物，具有全新的酞菁类化合物的基本结构，表现出一系列已有的酞菁类化合物所不具备的新的性质。这些性质是：UV-VIS-NIR吸收光谱具有三个强吸收峰，其中最有特征的是1428nm处时附近出现的近红外吸收；表面光伏特性；光致发光特性；电致发光特性；超高的热稳定性；良好的导电性等。
这类分子所具有的一系列独特的性质，使得该类化合物在众多重要领域中具有潜在的作用。例如，该类化合物表现出的近红外光电活性，可使该类化合物成为一种近红外光电材料，用于制备近红外光电器件等；该类化合物有序超薄薄膜所表现出的良好的导电各向异性，可用于制备分子器件线路的分子导线；该类化合物表现出的光致发光和电致发光特性，可用于制备有机显示器件等。另外，由于该类化合物在分子结构上所具有的特征，例如，在一个大的紫菜嗪环中有两个金属离子，使通式(2)化合物能拥有一个庞大的衍生物群体。因为，具有四个异吲哚亚单元的紫菜嗪环可以与七十余种元素结合。如果从七十余种元素中取出二种不同元素进行组合进行通式(2)化合物的合成，仅仅由于中心离子的改变，将得到通式(2)化合物二千五百多种衍生物。通过在与紫菜嗪环并接的外围芳香环上引入取代基，将使衍生物的数目剧增。这种拥有数目众多衍生物的通式(2)化合物将构成酞菁类化合物家族中重要的一族。本发明对推动化学、材料科学、信息科学等领域的发展具有重要的意义。
附图说明
图1、化合物1的结构通式(1)。
图2、化合物2的结构通式(2)。
图3、化合物3的结构通式(3)。
图4、化合物1a1的分子结构图。
图5、化合物1a1的NMR谱图。
图6、化合物1a1的STM图像。
图7、化合物1a1的模拟图像。
图8、化合物2a1的分子结构图。
图9、化合物2a1的MS谱图。
图10、化合物2a1的H1NMR谱图。
图11、化合物2a1的H1C13NMR谱图。
图12、化合物2a1的XPS谱图。
图13、化合物2a1的STM图像。
图14、化合物2a1的STM 3D图像。
图15、化合物2a1的模拟图。
图16、化合物2a1的UV-VIS-NIR吸收光谱。
图17、化合物2a1的光致发光谱(近红外区)。
图18、化合物2a1的光致发光谱(可见区)。
图19、化合物2a1的表面光电压谱。
图20、化合物2a1在ITO玻璃上薄膜的三维FAM图像。
图21、化合物1a2的结构图。
图22、化合物2a2的结构图。
图23、化合物1a3的结构图。
图24、化合物2a3的结构图。
具体实施方式
实施例1化合物1a1的合成
选择通式(1)中A1和A4代表氮原子，A2和A3代表碳原子，R1和R4不代表任何基团和原子，R2和R3代表氢原子，M代表Cu(II)离子，R5…R6代表
I，II，III部分的结构相同，构成化合物1a1，结构式为图4。
称取尿素8.0001g，通式(3)化合物如：2，3-吡嗪二甲酸(Pyrazine-2，3-dicarboxylic Acid)4.0008g(0.0238mol)，CuCl2·2H2O1.3683g(0.0080mol)，(NH4)2MoO40.8001g研细混合均匀后装入带有聚四氟乙烯衬里的钢弹中密封，将钢弹放入烘箱中加热至240℃8小时；待钢弹冷却至室温开盖，取出黑色固体；将该黑色固体放入真空提纯装置中，在10-4Pa，300℃条件下提纯24小时。经过上述操作制得了通式(1)化合物1a1。质谱仪测得分子离子峰(图5)M+：537.9452amu，与计算值537.9472相吻合。用超高真空的STM获得了化合物1a1的单分子图像(图6)，该图像与计算机模拟结果(图7)相符合。
实施例2化合物2a1的合成
选择通式(1)中A1和A4代表氮原子，A2和A3代表碳原子，R1和R4不代表任何基团和原子，R2和R3代表氢原子，M代表Cu(II)离子，I、II、III、IV、V、VI的结构相同，构成通式(2)化合物2a1，结构式为图8
将制得的通式(1)化合物1a1放入真空装置中，在10-4Pa，500℃条件下反应24小时，发生通式(1)化合物1a1的双分子缩合反应后，制得了通式(2)化合物2a1。质谱仪测得通式(2)化合物2a1的分子离子峰(图9)M+Na+：931.9193amu，与计算值930.7240相接近，与M+H+Na+的计算值931.7319相符合。这归结为在质谱仪中的氢气与通式(2)化合物2a1在等离子体的环境中发生反应。通式(2)化合物2a1的NMR谱(图10、11)、XPS(图12)谱、和STM单分子图像(图13、14、15)进一步确定了通式(2)化合物2a1的分子结构。XPS谱测得通式(2)化合物2a1的元素有C、N、H、Cu，NMR的H1谱确定了通式(2)化合物2a1中氢的种类和数量，NMR的C13谱确定了通式(2)化合物2a1中C的种类，STM分子图像确定了通式(2)化合物2a1的分子构型。
实施例3通式(2)化合物2a1的UV-VIS-NIR吸收光谱
采用UV-VIS-NIR光谱仪研究通式(2)化合物2a1甲酸溶液的UV-VIS-NIR吸收光谱(图16)、，结果表明，它除了具有一般酞菁所共同具有的紫外区和可见区的吸收峰外，出现了一个在近红区(1.428μm)的吸收，吸光系数很大。我们所观察到的通式(2)化合物2a1的UV-VIS-NIR吸收光谱与一般酞菁有很大的差别。应用这一性质可用通式(2)化合物制备光电器件，特别是近红外光电器件。通式(2)化合物2a1近红外区的光活性用于癌症的红外光动力治疗时，利用近红外线对人体的穿透特性，在体外照射可完成光的传输过程。这一特性还可以用于环保领域中有害物质测定所用气敏传感器材料的制备
实施例4通式(2)化合物2a1的光致发光谱(荧光光谱)
使用荧光光谱仪在10K的温度条件下分别用1200nm和350nm波长的激发光激发化合物2a1，测量化合物2a1的荧光光谱(图17、18)。结果表明该化合物在1530nm的近红外区和450nm的可见光区发射荧光。应用这一性质可用化合物2制备发光器件，特别是近红外发光器件。
实施例5化合物2a1的光伏特性(表面光电压谱SPS)
用表面光电压谱仪测得化合物2a1的光伏特性曲线，即表面光电压谱(图19)。结果表明化合物2a1的光伏特性非常明显，并在近红外区大约在1100nm左右也出现光伏特性。应用这一性质可用化合物2制备基于光电转换原理的器件。
实施例6化合物2a1的超高的热稳定性
将化合物2a1在10-4～10-10Pa，900℃条件下进行真空镀膜，对生成的膜物质进行质谱、核磁和XPS表征，发现该化合物2a1仍然存在。这表明该化合物具有超高的热稳性。应用这一性质可用化合物2制备在高温环境中工作的光电器件，用于航天航空等领域。
实施例7化合物2a1溥膜的导电性
在实施例6的条件下，将化合物2a1蒸镀到ITO玻璃上，得到100nm左右厚度的溥膜(图20)。测定溥膜的电导率为4×105Ω-1cm-1。应用这一性质可用化合物2制备分子器件中的导电材料，用于信息工程领域。
实施例8通式(1)化合物1a2的合成
选择通式(1)中A1和A4代表氮原子，A2和A3代表碳原子，R1和R4不代表任何基团和原子，R2和R3代表氢原子，M代表Co(II)离子，R5…R6代表
I，II，III部分的结构相同，构成化合物1a2，结构式为图21。
称取尿素8.0001g，通式(1)化合物如：2，3-吡嗪二甲酸(Pyrazine-2，3-dicarboxylic Acid)4.0008g(0.0238mol)，CoCl2·6H2O1.8876g(0.0080mol)，(NH4)2MoO40.8001g研细混合均匀后装入带有聚四氟乙烯衬里的钢弹中密封。将钢弹放入烘箱中加热至240℃8小时。待钢弹冷却至室温开盖，取出黑色固体。将该黑色固体放入真空提纯装置中，在10-4Pa，300℃条件下提纯24小时。经过上述操作制得了化合物1a1。质谱仪测得分子离子峰M+：533.3452amu，与计算值533.3344相吻合。
实施例9通式(2)化合物1a22a2的合成与表征
选择通式(1)中A1和A4代表氮原子，A2和A3代表碳原子，R1和R4不代表任何基团和原子，R2和R3代表氢原子，M1代表Cu(II)离子，M1代表Co(II)离子，I、II、III、IV、V、VI的结构相同，构成化合物2a1，结构式为图22。
将制得的化合物1a1和化合物1a2按摩尔比为1/1混合后放入真空装置中，在10-4Pa，550℃条件下反应28小时，发生化合物1a1和化合物1a2的双分子交叉缩合反应后，制得了化合物2a2。质谱仪测得化合物2a2的分子离子峰M+Na+：985.2193amu，与计算值985.1241相符合。
实施例10通式(1)化合物1a3的合成与表征
选择通式(1)中A1、A2、A3和A4代表碳原子，R1和R3，和R4代表氢原子，R2代表硝基，M代表Ni(II)离子，R5…R6代表
I，II，III部分的结构相同，构成化合物1a3，结构式为图23。称取尿素8.0001g，4-硝基邻苯二甲酸(4-Nitro-phthalic acid)5.0460g(0.0239mol)，NiSO4·7H2O 2.242g(0.0080mol)，(NH4)2MoO40.8001g研细混合均匀后装入带有聚四氟乙烯衬里的钢弹中密封。将钢弹放入烘箱中加热至250℃18小时。待钢弹冷却至室温开盖，取出黑色固体。将该黑色固体放入真空提纯装置中，在10-4Pa，300℃条件下提纯24小时。经过上述操作制得了化合物1a3。质谱仪测得分子离子峰M+：662.1655amu，与计算值662.1588相吻合。
实施例11通式(2)化合物2a3的合成与表征
选择通式(1)中A1和A4代表氮原子，A2和A3代表碳原子，R1和R4不代表任何基团和原子，R2和R3代表氢原子，M1代表Cu(II)离子，A`1、A`2、A`3和A`4代表碳原子，R`1、R`3，和R`4代表氢原子，R2代表硝基，M2代表Ni(II)离子，结构式为图24。
将制得的化合物1a1和化合物1a3按摩尔比为1/1混合后放入真空装置中，在10-4Pa，500℃条件下反应8小时，发生化合物1a1和化合物1a3的双分子交叉缩合反应后，制得了化合物2a3。质谱仪测得化合物2a3的分子离子峰M+Na+1054.9367amu，与计算值1054.9356相符合。
Claims (9)
1. 下述化合物1a1，具有以下结构：
2. 下述化合物2a1，具有以下结构：
3. 权利要求1所述化合物1a1的制备方法：
称取尿素8.0001g，2，3-吡嗪二甲酸4.0008g，CuCl22H2O 1.3683g，(NH4)2MoO40.8001g研细混合均匀后装入带有聚四氟乙烯衬里的钢弹中密封，将钢弹放入烘箱中加热至240℃8小时；待钢弹冷却至室温开盖，取出黑色固体；将该黑色固体放入真空提纯装置中，在10-4Pa，300℃条件下提纯24小时，得化合物1a1。
4. 权利要求2所述化合物2a1的制备方法，包括以下步骤：
将权利要求1所述的化合物1a1装入一个带有真空和可以加热的反应装置中，在10-4～10-10Pa，400～600℃条件下反应8～48小时，发生双分子缩合后得到化合物2a1。
5. 权利要求2所述化合物2a1用于环保领域中有害物质测定所用气敏传感器材料的制备。
6. 权利要求2所述化合物2a1在制备近红外发光器件的应用。
7. 权利要求2所述化合物2a1在制备光电转换原理的器件的应用。
8. 权利要求2所述化合物2a1在制备高温环境中工作的光电器件的应用。
9. 权利要求2所述化合物2a1在制备分子器件中的导电材料的应用。
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| PCT/CN2004/000109 WO2004072082A1 (fr) | 2003-02-11 | 2004-02-09 | Composes de superphtalocyanine contenant six sous-unites isoindole dans le cycle porphyrazine, leurs procedes de preparation et utilisations |
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| CN102533247B (zh) * | 2010-12-12 | 2015-09-30 | 陈文通 | 一种含镝荧光晶体及其制备方法 |
| CN105733293B (zh) * | 2012-06-18 | 2017-06-27 | 日本化药株式会社 | 紫菜嗪色素及其用途 |
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| CN1150166A (zh) * | 1995-05-12 | 1997-05-21 | 西巴-盖尔基股份公司 | 结构化颜料涂料及其制备和用途 |
| WO2001042368A1 (en) * | 1999-12-08 | 2001-06-14 | Gentian As | Substituted phthalocyanines and their precursors |
| CN1344718A (zh) * | 2001-07-30 | 2002-04-17 | 宾月景 | 新型酞菁衍生物及其应用 |
| CN1356328A (zh) * | 2001-09-05 | 2002-07-03 | 东北师范大学 | 四－(1,4,8,9－四氮杂)苯并菲类金属酞菁化合物及合成方法 |
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| US4839112A (en) * | 1982-12-20 | 1989-06-13 | Northwestern University | Methods for fabricating a low dimensionally electroconductive article |
| JPH02187468A (ja) * | 1989-01-17 | 1990-07-23 | Japan Carlit Co Ltd:The | フタロシアニン化合物 |
| JPH05163440A (ja) * | 1991-12-16 | 1993-06-29 | Japan Carlit Co Ltd:The | フタロシアニン化合物 |
| JP3959143B2 (ja) * | 1996-12-26 | 2007-08-15 | 株式会社日本触媒 | 新規フタロシアニン化合物、その製造方法および近赤外吸収材料 |
| GB9714905D0 (en) * | 1997-07-16 | 1997-09-17 | Johnson Matthey Plc | Photosensitizers |
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| CN1150166A (zh) * | 1995-05-12 | 1997-05-21 | 西巴-盖尔基股份公司 | 结构化颜料涂料及其制备和用途 |
| WO2001042368A1 (en) * | 1999-12-08 | 2001-06-14 | Gentian As | Substituted phthalocyanines and their precursors |
| CN1344718A (zh) * | 2001-07-30 | 2002-04-17 | 宾月景 | 新型酞菁衍生物及其应用 |
| CN1356328A (zh) * | 2001-09-05 | 2002-07-03 | 东北师范大学 | 四－(1,4,8,9－四氮杂)苯并菲类金属酞菁化合物及合成方法 |
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| WO2004072082A1 (fr) | 2004-08-26 |
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