CN105418521A - 二(4-(4h-1,2,4-三唑-4-基)苯基)硫化合物及其应用 - Google Patents
二(4-(4h-1,2,4-三唑-4-基)苯基)硫化合物及其应用 Download PDFInfo
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- LIZVUWIHFCQRPY-UHFFFAOYSA-N 4-[4-[4-(1,2,4-triazol-4-yl)phenyl]sulfanylphenyl]-1,2,4-triazole Chemical compound N=1N=CN(C=1)C1=CC=C(C=C1)SC1=CC=C(C=C1)N1C=NN=C1 LIZVUWIHFCQRPY-UHFFFAOYSA-N 0.000 title abstract 5
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- GBBFUAZDRBBUQG-UHFFFAOYSA-N N=1N=CN(C=1)C1=CC=C(C=C1)[S] Chemical compound N=1N=CN(C=1)C1=CC=C(C=C1)[S] GBBFUAZDRBBUQG-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- -1 (4-(4H-1,2,4-triazole-4-yl) phenyl) sulphur compound Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005260 alpha ray Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011701 zinc Substances 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 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
- 239000012453 solvate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
本发明公开了二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物及其应用。同时也公开了单晶的制备方法，它是采用二(4-(4H-1,2,4-三唑-4-基)苯基)硫溶解在甲醇中常温挥发得到的。本发明进一步公开了二(4-(4H-1,2,4-三唑-4-基)苯基)硫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？=？330？nm，发射波长<i>λ</i>ex？=？550？nm。二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶与Zn(Ac)2·2H2O结合可以制成一维锌配合物。
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，涉及二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物及其单晶的制备方法与应用。
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，尚未查到二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶结构。
发明内容
本发明的一个目的在于提供一种二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物、单晶及其制备方法。
为此本发明人提供了如下的技术方案：
二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物具有如下的结构：
二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶，其特征在于该单晶结构采用APEXIICCDareadetector，使用经过石墨单色化的Mokα射线(λ=0.71073?)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：
本发明所述二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶的制备方法，其特征在于将二(4-(4H-1,2,4-三唑-4-基)苯基)硫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二(4-(4H-1,2,4-三唑-4-基)苯基)硫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λ ex=330nm，发射波长λ ex=550nm。所述的制备发光材料中间体指的是：化合物与Zn(Ac)2·2H2O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550nm。
(2)说明本发明制成的单晶和Zn(Ac)2·2H2O结合可以制成一维锌金属配合物。
附图说明：
图1为二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物结构图。
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。所有的原料都是从国内外的化学试剂公司进行购买，其中的4-(4-氨基苯硫基)苯胺、双甲酰肼均有市售，没有经过继续提纯而是直接使用的。
实施例1
4-(4-氨基苯硫基)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50mL三口圆底烧瓶内分别加入4-(4-氨基苯硫基)苯胺(1mmol)和双甲酰肼(4mmol)，开动搅拌在150oC，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100mL热甲醇，搅拌溶解后，过滤，滤液缓慢挥发得到紫色固体，收率85%。
实施例2
二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶的制备方法
将二(4-(4H-1,2,4-三唑-4-基)苯基)硫(1mmol)溶解在CH3OH(20mL)中，搅拌五分钟后过滤，滤液在常温下挥发两天得到适合X-射线单晶衍射的块状晶体。元素分析(C16H12N6S)实测值：C60.02；H3.82；N26.32。理论值：C59.98；H3.78；N26.23。
实施例3
二(4-(4H-1,2,4-三唑-4-基)苯基)硫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2）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350nm和500nm。
步骤：将二(4-(4H-1,2,4-三唑-4-基)苯基)硫研磨压片成外径为27mm、厚度约3mm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λ ex=350nm，发射波长λ ex=500nm。
实施例4
和金属组成配合物的应用实例：
二(4-(4H-1,2,4-三唑-4-基)苯基)硫(L)(0.1mmol)和Zn(Ac)2·2H2O(0.1mmol)在水(10mL)中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的紫色块状晶体。产率：40%。元素分析(C20H22N6O6SZn)理论值(%)：C，44.49；H，4.11；N，15.57。实测值：C，44.56；H，4.17；N，15.49。
为了确切了解染料在TiO2膜上的吸附量，将实施例4制备的配合物单晶染料敏化TiO2纳米晶膜(几何面积约为1cm2)浸泡在10mL0.01mol·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1.4×10-3mol/cm2。
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)
1.二(4-(4H-1,2,4-三唑-4-基)苯基)硫具有如下的结构：
。
2.二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶，其特征在于该单晶结构采用APEXIICCDareadetector，使用经过石墨单色化的Mokα射线λ=0.71073?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所述二(4-(4H-1,2,4-三唑-4-基)苯基)硫单晶的制备方法，其特征在于二(4-(4H-1,2,4-三唑-4-基)苯基)硫化合物在CH3OH溶剂中常温挥发法得到的。
4.二(4-(4H-1,2,4-三唑-4-基)苯基)硫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λ ex=330nm，发射波长λ ex=550nm。
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(Ac)2·2H2O结合制成一维锌配合物。
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