CN103694264B - 一种巯基氮杂环化合物及其制备方法 - Google Patents
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Abstract
本发明涉及配位聚合物材料领域，具体涉及一种巯基氮杂环化合物及其制备方法。一种巯基氮杂环化合物，化学式为C8H10Cd2Cl2N6OS4；所述巯基氮杂环化合物为四方晶系，<i>P-421c</i>空间群，晶胞参数为<i>a？</i>=11.3795(8)？，<i>？c？</i>=14.1889(19)？，V？=1837.4(3)？3。本发明的巯基氮杂环化合物易于制备，而在溶剂热情况下能够发生原位反应，合成出来的材料缺陷少，结晶度高。这种巯基氮杂环化合物在催化、传感、分子识别、分子发光等领域有非常好的潜在的应用前景。
Description
技术领域
本发明涉及配位聚合物材料领域，具体涉及一种巯基氮杂环化合物及其制备方法。
背景技术
近年来，人们深刻地意识到了硫在化学和生物过程中的重要性，巯基氮杂环配体含有–N(H)–C(=S)或–N–C–(SH)功能团，使得含S原子的有机化合物具有结构的多样性，并呈现出新颖的化学性质和光谱性质。化学家对其感兴趣是因为它是潜在的多齿配体，其环外S原子和杂环N原子都是潜在的配位点，它们经常被用来研究与Lewis软酸如Cd(II)、Cu(I)、Ag(I)的配位特性，其配位形式多种多样，灵活易变。近来，化学家们围绕镉盐、铜盐、银盐和巯基氮杂环配体合成了一系列基于巯基氮杂环配体的配合物材料，在磁性分子、有机导电体和分子光电器件等方面的应用引人注目。利用硫原子作为桥联配体将过渡金属连接起来更容易得到一些簇单元，而且由于这些过渡金属的轨道能量与硫原子的相匹配，由这些簇单元构筑的配位聚合物一般都有很好的光学性质。在水热合成配合物的过程中，由于反应物处在剧烈的高温和高压下，有机反应物活性位点可能会被激活，能发生常温下未见过的有机反应。这是一种很新颖的得到巯基氮杂环化合物的新方法。
发明内容
本发明的目的在于提供一种巯基氮杂环化合物。
本发明的另一个目的在于提供上述巯基氮杂环化合物的制备方法。
本发明所要解决的技术问题通过以下技术方案予以实现：
一种巯基氮杂环化合物，化学式为C8H10Cd2Cl2N6OS4；所述巯基氮杂环化合物为四方晶系，P-421c空间群，晶胞参数为a=11.3795(8)?，c=14.1889(19)?，V=1837.4(3)?3。
优选的，Cd原子采取六配位八面体构型，与两个S原子、两个N原子和两个Cl原子配位，Cd?S键长分别为2.678(3)，2.690?；Cd-N的键长分别为2.392(7)，2.389(7)?；Cd-Cl的键长分别为2.555(2)，2.618(3)?。
该巯基氮杂环化合物的制备方法为：将有机配体三聚硫氰酸、CdCl2?4H2O、乙腈和水的混合物在室温下搅拌，然后将所述混合物在溶剂热条件下加热反应后缓慢降温得到巯基氮杂环化合物。
优选的，所述的加热温度为140℃~180℃，加热反应时间为24~72小时。
优选的，所述的降温为2℃/小时~5℃/小时降至室温。
优选的，所述的乙腈和水的体积比为4:1~6:1。
优选的，所述三聚硫氰酸与CdCl2?4H2O的摩尔比为0.5:1.0~1.0:2.0。
优选的，所述三聚硫氰酸与CdCl2?4H2O的摩尔比优选为1.0~1.0。
本发明的巯基氮杂环化合物从晶体结构来看，在溶剂热反应后三聚硫氰酸发生了有机反应，得到了新的配体6-甲基-1,3,5-三嗪-2,4-二硫醇。因为溶剂热体系反应非常剧烈，乙腈分子裂解产生甲基自由基，与活化的原配体发生自由基反应形成6-甲基-1,3,5-三嗪-2,4-二硫醇，而这种巯基氮杂环化合物在分子发光领域有非常好的潜在的应用前景。
本发明具有如下有益效果：
本发明的巯基氮杂环化合物易于制备，而在溶剂热情况下能够发生原位反应，合成出来的材料缺陷少，结晶度高。
这种巯基氮杂环化合物在催化、传感、分子识别、分子发光等领域有非常好的潜在的应用前景。
附图说明
图1为本发明的巯基氮杂环化合物C8H10Cd2Cl2N6OS4以金属中心Cd(II)的配位环境图。
图2为本发明的巯基氮杂环化合物C8H10Cd2Cl2N6OS4由Cl双桥连接成的双股链结构图。
具体实施方式
下面通过实施例对本发明做进一步详细说明，这些实施例仅用来说明本发明，并不限制本发明的范围。
实施例1
将1mmol的三聚硫氰酸与1mmolCdCl2?4H2O溶解于10mL乙腈和2mL蒸馏水的混合溶液中，常温搅拌20min，随后转移到聚四氟乙烯高压反应釜中，将其放在160℃烘箱中反应72小时，之后以5℃/小时降至室温过滤得到巯基氮杂环化合物C8H10Cd2Cl2N6OS4，产率49.5%。
然后将上述簇基配位聚合物进行结构表征
晶体1的X射线衍射数据是在BrukerSmartApexCCD面探衍射仪上，用MoK a辐射(λ=0.71073?)，以w扫描方式收集并进行Lp因子校正，吸收校正使用SADABS程序。用直接法解结构，然后用差值傅立叶法求出全部非氢原子坐标，并用理论加氢法得到氢原子位置(C?H1.083?)，用最小二乘法对结构进行修正。计算工作在PC机上用SHELXTL程序包完成。详细的晶体测定数据见表1。结构见图1，图2。
表1
| formula | C8H10Cd2Cl2N6OS4 |
| Formula weight | 630.16 |
| temp / K | 293(2) |
| cryst syst | tetragonal |
| space group | P-421c |
| a/ ? | 11.3795(8) |
| b/ ? | 11.3795(8) |
| c/ ? | 14.1889(19) |
| α/ o | 90.00 |
| β/ o | 90.00 |
| γ/ o | 90.00 |
| V/ ?3 | 1837.4(3) |
| Z | 4 |
| Dc/ g cm-3 | 2.278 |
| μ/ mm-1 | 3.068 |
| F(000) | 1208 |
| No. of rflns collected | 4601 |
| No. of Indep rflns | 1556 |
| R int | 0.0416 |
| GOF | 1.127 |
| R1a (I > 2σ(I)) | 0.0473 |
| wR2a (all data) | 0.1172 |
a R 1=?||F o|-|F c||/?|F o|,wR 2=[?w(F o 2-F c 2)2/?w(F o 2)2]1/2
实施例2
将0.5mmol的三聚硫氰酸与2mmolCdCl2?4H2O溶解于12mL乙腈和2mL蒸馏水的混合溶液中，常温搅拌20min，随后转移到聚四氟乙烯高压反应釜中，将其放在180℃烘箱中反应24小时，之后以2℃/小时降至室温过滤得到巯基氮杂环化合物C8H10Cd2Cl2N6OS4，产率33.2%。
实施例3
将1mmol的三聚硫氰酸与1.5mmolCdCl2?4H2O溶解于8mL乙腈和2mL蒸馏水的混合溶液中，常温搅拌15min，随后转移到聚四氟乙烯高压反应釜中，将其放在140℃烘箱中反应48小时，之后以4℃/小时降至室温过滤得到巯基氮杂环化合物C8H10Cd2Cl2N6OS4，产率35.2%。
实施例4
将0.5mmol的三聚硫氰酸与1mmolCdCl2?4H2O溶解于9mL乙腈和2mL蒸馏水的混合溶液中，常温搅拌25min，随后转移到聚四氟乙烯高压反应釜中，将其放在170℃烘箱中反应60小时，之后以3℃/小时降至室温过滤得到巯基氮杂环化合物C8H10Cd2Cl2N6OS4，产率37.5%。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应落在本发明的保护范围之内。
Claims (3)
1.一种巯基氮杂环化合物，其特征在于：化学式为C8H10Cd2Cl2N6OS4；所述巯基氮杂环化合物为四方晶系，P-421c空间群，晶胞参数为a=11.3795(8)?，c=14.1889(19)?，V=1837.4(3)?3，Cd原子采取六配位八面体构型，与两个S原子、两个N原子和两个Cl原子配位，Cd?S键长分别为2.678(3)，2.690?；Cd-N的键长分别为2.392(7)，2.389(7)?；Cd-Cl的键长分别为2.555(2)，2.618(3)?，其结构式如下所示：
。
2.权利要求1所述的一种巯基氮杂环化合物的制备方法，其特征在于：将有机配体三聚硫氰酸、CdCl2?4H2O、乙腈和水的混合物在室温下搅拌，然后将所述混合物在溶剂热条件下加热反应后缓慢降温得到巯基氮杂环化合物，其中所述的加热温度为140℃~180℃，加热反应时间为24~72小时，所述的降温为2℃/小时~5℃/小时降至室温，所述的乙腈和水的体积比为4:1~6:1，所述三聚硫氰酸与CdCl2?4H2O的摩尔比为0.5:1.0~1.0:2.0。
3.根据权利要求2所述的一种巯基氮杂环化合物的制备方法，其特征在于：所述三聚硫氰酸与CdCl2?4H2O的摩尔比优选为1.0~1.0。
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| CN1226235A (zh) * | 1996-05-21 | 1999-08-18 | 拜尔公司 | 巯基－咪唑基衍生物及其作为杀微生物剂的用途 |
| CN1589307A (zh) * | 2001-10-17 | 2005-03-02 | 通用显示公司 | 磷光化合物及包括该磷光化合物的元件 |
| CN1970562A (zh) * | 2006-10-24 | 2007-05-30 | 中国科学技术大学 | 金属－芳香基硫化物纳米纤维材料及制备方法 |
| WO2012012495A2 (en) * | 2010-07-20 | 2012-01-26 | The Regents Of The University Of California | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1066677A (zh) * | 1991-05-13 | 1992-12-02 | 鲁布里佐尔公司 | 含铜有机金属配合物和含有这种配合物的浓缩物及柴油燃料 |
| CN1226235A (zh) * | 1996-05-21 | 1999-08-18 | 拜尔公司 | 巯基－咪唑基衍生物及其作为杀微生物剂的用途 |
| CN1589307A (zh) * | 2001-10-17 | 2005-03-02 | 通用显示公司 | 磷光化合物及包括该磷光化合物的元件 |
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| WO2012012495A2 (en) * | 2010-07-20 | 2012-01-26 | The Regents Of The University Of California | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
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