CN105418522A - 1,4-二(4-(1h-1,2,4-三唑-1-基)苯基)哌嗪单晶及应用 - Google Patents
1,4-二(4-(1h-1,2,4-三唑-1-基)苯基)哌嗪单晶及应用 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 15
- KCFWYCCOYXRKGT-UHFFFAOYSA-N 1,4-bis[4-(1,2,4-triazol-1-yl)phenyl]piperazine Chemical compound N1(N=CN=C1)C1=CC=C(C=C1)N1CCN(CC1)C1=CC=C(C=C1)N1N=CN=C1 KCFWYCCOYXRKGT-UHFFFAOYSA-N 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
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- 239000000463 material Substances 0.000 claims abstract description 6
- -1 4-(1H-1,2,4-triazol-1-yl) phenyl Chemical group 0.000 claims description 18
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
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- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical class NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
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- 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
- 238000000227 grinding Methods 0.000 description 1
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- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明公开了1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶及其制备方法，它是采用1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪溶解在甲醇中常温挥发得到的。本发明进一步公开了1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶在制备作为发光材料中间体方面的应用，该化合物的激发波长<i>λ</i>ex=330nm，发射波长<i>λ</i>ex=550nm。
Description
本发明得到国家自然科学基金面上项目(21471113)、天津市教委面上项目(20140506)和天津师范大学中青年教师学术创新推进计划项目(52XC1401)的资助。
技术领域
本发明属于有机合成技术领域，涉及1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶的制备方法及应用。
背景技术
1,2,4-三唑及其衍生物兼有吡唑和咪唑的配位特点，是配位能力较强的桥连配体，目前已合成并表征了大量的单核、多核和多维化合物。这些配体能够以1,2位上的氮原子与金属离子配位形成N1,N2-桥连模式，对于4位未取代的1,2,4-三唑衍生物能通过2,4位上的氮原子形成N2,N4-桥连模式，这种N2,N4-桥连模式同金属酶中咪唑的N1,N3-桥连模式类似。对于三唑类化合物的特殊用途还表现在分子器件化的设计上，合成具有不同维数的金属配合物乃是完成器件化至关重要的一步。迄今为止，尚未查到1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶结构。
发明内容
本发明的一个目的在于提供一种1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶及其制备方法。
为此本发明人提供了如下的技术方案：
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪化合物具有如下的结构：
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶，其特征在于该单晶结构采用APEXII CCD area detector，使用经过石墨单色化的Mokα射线(λ = 0.71073 Å)为入射辐射，以ω-2θ扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值Fourier电子密度图利用SHELXL-97直接法解得单晶数据：：
本发明所述1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶的制备方法，其特征在于将1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪化合物溶于甲醇溶剂中，采用常温挥发法得到棒状晶体。
本发明进一步公开了1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶在制备作为发光材料中间体方面的应用，该化合物的激发波长λex = 330 nm，发射波长λex = 550nm。所述的制备发光材料中间体指的是：化合物与Zn(NO3)2·6H2O和对苯二甲酸结合制成一维锌配合物。
实验结果显示制成的这个金属配合物有如下的特点：
(1) 配合物单晶染料在TiO2膜上的吸收光谱均明显变宽和红移。这表明染料分子在TiO2形成了首并尾的J-聚集体。从DSCs的工作原理讲，染料聚集引起的光谱宽化和红移对于染料的光电响应范围的拓宽是十分有利的。但与此同时，染料聚集体会大大降低其电子注入效率，从而导致DSCs的性能低下。所以，通常在染料溶液中加入共吸附剂来抑制染料的聚集。该配合物单晶在甲醇溶液中及其在TiO2膜电极上的紫溶液的荧光测试采用2.5×10-5mol/L的甲醇溶液，最大荧光发射波长位于550 nm。
(2) 说明本发明制成单晶和Zn(NO3)2·6H2O和对苯二甲酸结合可以制成一维锌金属配合物。
附图说明：
图1为1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪结构式。
具体实施方式
下面结合实施例对本发明做进一步的说明，实施例仅为解释性的，决不意味着它以任何方式限制本发明的范围。所有的原料例如4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺、双甲酰肼等都是从国内外的化学试剂公司进行购买，没有经过继续提纯而是直接使用的。
实施例1
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪(L)的制备
4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺：双甲酰肼的摩尔比为1:4
在装有磁子、回流冷凝器和温度计的50 mL三口圆底烧瓶内分别加入4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺(1 mmol)和双甲酰肼(4 mmol)，开动搅拌在150 oC，反应24小时。反应结束后，将反应液降至室温，将得到的沉淀加入100 mL热甲醇，搅拌溶解后，过滤，滤液缓慢挥发得到白色固体，收率85%；
4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺双甲酰肼。
本发明优选4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺和双甲酰肼的摩尔比为1:4；反应温度150℃，反应时间24小时。采用“一锅法”，将4-((4-(4-氨基苯基)哌嗪-1-基)甲基)苯胺和双甲酰肼在加热条件下制备1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪(L)。
实施例2
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶的制备方法。
将1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪(1 mmol)溶解在CH3OH(20 mL)中，搅拌五分钟后过滤，滤液在常温下挥发两天得到适合X-射线单晶衍射的无色块状晶体。元素分析(C22N8H24) 理论值(%)：C，65.98；H，6.04；N，29.98。实测值：C，65.88；H，6.05；N，30.05。
实施例3
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪(L) (0.1 mmol)、对苯二甲酸(tpa) (0.1mmol)和Zn(NO3)2·6H2O (0.1 mmol)在水(10 mL)中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的无色块状晶体。产率：40%。元素分析(C38H42N8O12Zn) 理论值(%)：C，52.57；H，4.88；N，12.91。实测值：C，52.68；H，4.84；N，12.97。
实施例4
1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶作为制备发光材料中间体的应用。
方法：通过荧光分光光度计，分别进行该化合物（实施例1）的激发波长和发射波长的扫描，选择并确定最佳波长。
结论：该化合物的激发波长和发射波长分别为350 nm和500 nm。
步骤：将1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪研磨压片成外径为27 mm、厚度约3 mm的片状样品，放入MPF-4荧光光谱仪的样品池进行测量。
结果：该化合物的激发波长λex = 350 nm，发射波长λex = 500 nm。
实施例5
染料或发光剂使用的实际例子
方法：染料溶液的微分脉冲伏安(DPV)曲线通过美国普林斯顿应用研究所研制的PARSTAT 2273电化学工作站测量。溶液的DPV测试采用三电极体系，玻碳电极为工作电极，辅助电极为铂片电极，自制的Ag/AgNO3电极为参比电极；电解液为0.1mol·L-1TBAP的乙腈溶液。以二茂铁氧化还原可逆点对为内标，得到测试体系与标准氢电极体系之间的校正值。
单色入射光光电转换效率(IPCE)描述DSCs在单色光作用下的光电转换效率，是转移到外电路的电子数与入射光子数之比。测量时，使用500 W氙灯作为光源，入射光经过WDS-5型组合式多功能光栅光谱仪得到不同波长λ下的单色光；单色光照射于电池的光阳极，由Keithley2400数字源表读取电流值I。单色光的福照度由USB4000 plug-and-play微型光线光谱仪测量。
步骤：为了确切了解染料在TiO2膜上的吸附量，将实施例3制备的配合物单晶染料敏化TiO2纳米晶膜(几何面积约为1 cm2)浸泡在10 mL 0.01 mol·L-1的氢氧化钠的甲醇溶液中过夜，待染料完全解附后测定溶液的吸光度。根据吸光度和摩尔吸光洗漱可以计算出单位面积纳米晶膜上染料的吸附量。该配合物单晶的吸附量为1.4 × 10-3 mol/cm2。
结果：与染料的甲醇溶液相比，配合物单晶染料在TiO2膜上的吸收光谱均明显变宽和红移。这表明染料分子在TiO2形成了首并尾的J-聚集体。从DSCs的工作原理讲，染料聚集引起的光谱宽化和红移对于染料的光电响应范围的拓宽是十分有利的。但与此同时，染料聚集体会大大降低其电子注入效率，从而导致DSCs的性能低下。所以，通常在染料溶液中加入共吸附剂来抑制染料的聚集。该配合物单晶在甲醇溶液中及其在TiO2膜电极上的紫溶液的荧光测试采用2.5×10-5 mol/L的甲醇溶液，最大荧光发射波长位于500 nm。
在详细说明的较佳实施例之后，熟悉该项技术人士可清楚地了解，在不脱离上述申请专利范围与精神下可进行各种变化与修改，凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均属于本发明技术方案的范围。且本发明亦不受说明书中所举实例实施方式的限制。
Claims (5)
1.1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪具有如下的结构：
。
2.1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶，其特征在于该单晶结构采用APEXII CCD area detector，使用经过石墨单色化的Mokα射线，λ = 0.71073 Å为入射辐射，以ω-2θ 扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值Fourier电子密度图利用SHELXL-97直接法解得单晶数据：
。
3.权利要求2所述1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶的制备方法，其特征在于1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪化合物在CH3OH溶剂中常温挥发法得到的。
4.1,4-二(4-(1H-1,2,4-三唑-1-基)苯基)哌嗪单晶在制备作为发光材料中间体方面的应用，该化合物的激发波长λex = 330 nm，发射波长λex = 550 nm。
5.权利要求4所述的应用，其中所述的制备发光材料中间体指的是：该化合物与Zn(NO3)2·6H2O和对苯二甲酸结合制成一维锌配合物。
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