CN114409683B - 一种簇基银碘化合物、其制备方法及应用 - Google Patents
一种簇基银碘化合物、其制备方法及应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 13
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 13
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- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 thiophenol anions Chemical class 0.000 claims abstract description 3
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- IVCMUVGRRDWTDK-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1 IVCMUVGRRDWTDK-UHFFFAOYSA-M 0.000 claims description 10
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 8
- OTUQZYKBLAIJGU-UHFFFAOYSA-N benzenethiol;silver Chemical compound [Ag].SC1=CC=CC=C1 OTUQZYKBLAIJGU-UHFFFAOYSA-N 0.000 claims description 6
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- WIEPCLKFQFHUPU-UHFFFAOYSA-N 1-methyl-3-propyl-2h-imidazole;hydroiodide Chemical class I.CCCN1CN(C)C=C1 WIEPCLKFQFHUPU-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910003480 inorganic solid Inorganic materials 0.000 description 1
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- ZEQWBAHTKDTINN-UHFFFAOYSA-M silver benzenethiolate Chemical compound C1(=CC=CC=C1)[S-].[Ag+] ZEQWBAHTKDTINN-UHFFFAOYSA-M 0.000 description 1
- MSFPLIAKTHOCQP-UHFFFAOYSA-M silver iodide Chemical class I[Ag] MSFPLIAKTHOCQP-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明公开了一种新型簇基银碘化合物,所述化合物的化学式为[DabcoAg8I6(SPh)2],其中Dabco为三乙烯二胺,SPh‑为苯硫酚阴离子。该新型簇基银碘化合物的结构为三维“柱‑层”杂化骨架,其二维层Ag8I6(SPh)2由Ag8I6簇和µ 3‑SPh‑构建而成,层和层之间通过线性的Dabco配体扩展成3D的杂化骨架。本发明经试验发现:该化合物表现出特殊的荧光双发射现象,发射峰分别位于597 nm和787 nm处。该化合物在80‑260 K温度范围内表现出明显的热致荧光变色,是一种灵敏的强度型荧光温度传感材料。
Description
技术领域
本发明属于无机固体发光材料技术领域,具体涉及一种簇基银碘化合物、其制备方法及作为荧光温度传感器的应用。
背景技术
簇基金属卤化物具有多样的结构和优异的光电性质,在发光、传感、太阳能转换和光催化等领域具有广泛的应用前景,是一类重要的多功能晶态材料[Han, Z.-Y.; Sun,J.; He, H.Inorg. Chem.2021,60, 11081-11089; Jia, M.; Li, J.; Che,S.; Kan, L.;Li, G.; Liu, Y.Inorg. Chem. Front.2019,6, 1261-1266; Liu, J.-H.; Qi, Y.-J.;Zhao, D.; Li, H.-H.; Zheng, S.-T.Inorg. Chem.2019,58, 516-523;Xue, Y. Q.;Yang, X.; Sun, X.-L.; Lustig, W.P.; Mukherjee, S.; Rudd, N. D.; Desai, A. V.;Li, J.; Ghosh, S. K.Chem. Soc. Rev.2017,46, 3242-3285.]。
其中,Ag-I体系具有非常复杂多变的结构格外引人注目。Ag(I)具有d10电子构型,易于采用四面体配位模式AgI4四面体基本单元,AgI4基本单元可以以不同的聚合度聚合形成多种不同次级结构单元如Ag4I4、Ag5I6、Ag8I6等[Xue, Z.-Z.; Meng, X.-D.; Li, X.-Y.;Pan, J.; Wang, G.-M.Cryst. Growth Des.2021,21, 1055-1061; Song, D.-N.; Zhang,D.-J.; Wang, Y.-L.; Wang, J.-J.; Xing, X.-S.; Lv, Z.-Y.; Liu, F.; Han, J.-X.;Zhang, R.-C.; Liao, S.-J.;Zhang, R.Inorg. Chem.2020,59, 13067-13077; Yu, T.-L.; Guo, Y.-M.; Wu, G.-X.; Yang,X.-F.; Xue, M.; Fu, Y.-L.; Wang, M.-S.Coord. Chem. Rev.2019,397, 91-111;R.-C. Zhang,J.-J. Wang,B.-Q.Yuan,J.-C. Zhang,L.Zhou,H.-B. Yang,D.-J. Zhang,Y.-L. An,Inorg. Chem.2016, 55, 11593-11599.]。这些次级结构单元可以通过自聚合或有机配体连接组装成簇基银碘化合物骨架。所形成的化合物具有较高的共价性以及Ag和Ag之间有弱的金属---金属相互作用。这种独特的成键特征为新型簇基银碘化物的合成和性质的探索提供了前提。例如作为荧光材料,这类新型化合物具有发光强度高、Stock位移大、荧光寿命长等突出的优势,在传感、固态照明等诸多方面中有着重要的应用前景[Xue, Z.-Z.; Meng, X.-D.; Li,X.-Y.; Han, S.-D.; Pan, J.;Wang, G. M.Inorg. Chem.2021,60, 4375-4379; Liu, W.; Lustig, W. P.; Li,J.EnergyChem2019,100008;Li, S.-L.; Han, M.; Wu, B.; Wang, J.; Zhang, F.-Q.;Zhang, X.-M.Sci. Rep.2017,7, 13058P. Ford, A. Ogel,Acc. Chem. Res.1993, 26,220–226; H.-H. Li, Z.-R. Chen, J.-Q. Li.Eur. J. Inorg. Chem.2006,2447-2453.]。
研究簇基银碘化合物的合成,将极大地丰富无机合成化学、结构化学和材料化学,也为新型材料的合成机理的研究提供新途径。此外,研究簇基银碘化合物的合成,结构,发光性质及机理之间的关系,将为其他新型发光材料的开发提供新的思路[Xue, Z.-Z.;Meng, X.-D.; Li, X.-Y.; Han, S.-D.; Pan, J.; Wang, G. M.Inorg. Chem.2021,60,4375-4379; W Xin, B.; Sang, J.; Gao, Y.; Li, G.; Shi, Z.; Feng, S.RSC Adv.2018,8, 1973-1978; Liu, W.; Fang, Y.; Li, J.Adv. Funct. Mater.2018,28,1705593.; R.-C. Zhang,J.-J. Wang,J.-C. Zhang,M.-Q.Wang, M.S,F.-D, D.-J.Zhang, Y.-L.A,Inorg. Chem.2016, 55, 7556-7563.]。
发明内容
本发明目的在于提供一种簇基银碘化合物,所述化合物具有新颖的骨架结构,以及明显的热致荧光变色性质,可作为荧光材料应用。
本发明还提供了上述簇基银碘化合物的制备方法以及其作为荧光温度传感器的应用。
为实现上述目的,本发明采用如下技术方案:
一种簇基银碘化合物,其化学式为[DabcoAg8I6(SPh)2],其中,Dabco为三乙烯二胺,SPh-为苯硫酚阳离子。该簇基银碘化合物的结构表现为三维的“柱-层”杂化骨架,其二维Ag8I6(SPh)2层由Ag8I6簇和µ 3-SPh-构建而成,层和层之间通过线性的Dabco配体扩展成3D的杂化骨架。所述簇基银碘化合物的晶体属三方晶系,空间群为P31m,晶胞参数为:a=15.6316 Å (3) ,b= 15.6316 Å (3) ,c= 12.0038Å (5) ,α=β=90.0°,γ=120°。
上述的簇基银碘化合物的制备方法,其将苯硫酚银(AgSPh)、三乙烯二胺(Dabco)、1-丙基-3-甲基咪唑碘盐(PrImI)和溶剂超声分散以混合均匀,然后于60-120℃恒温反应120-180小时,反应结束后产物经洗涤、干燥即得。
具体的,所述苯硫酚银(AgSPh)、1-丙基-3-甲基咪唑碘盐(PrImI)、三乙烯二胺(Dabco)的摩尔比为1:2.5-4.0:1.0-2.7。AgSPh(silver thiophenolate),化学名称:苯硫酚银,其制备方法可参考文献 (Inorg. Chem.1991,30,183-187;Cryst. Growth Des.2009,9, 3821-3824)。
进一步优选的,所述溶剂为体积比2-4 : 1的乙腈-水混合液,优选乙腈-水体积比为3 : 1。溶剂的添加量可以为苯硫酚银(AgSPh)摩尔量的4-8倍,优选为4倍。
本发明提供了上述簇基银碘化合物作为荧光材料的应用。本发明经试验发现:上述簇基银碘化合物具有荧光性质,可作为荧光材料应用;进一步的,其还具有热致荧光变色行为,可作为温度传感材料应用。
本发明还提供了上述簇基银碘化合物作为荧光温度传感器的应用。本发明经试验进一步发现:上述簇基银碘化合物在80-260 K温度范围内表现出明显的热致荧光变色,位于597 nm和787 nm的发射峰的强度分别在80-260 K以及 80-200 K温度范围内对温度呈现好的线性关系,是一种灵敏的强度型荧光温度传感材料,可作为荧光变色温度传感器应用于荧光温度传感领域。
和现有技术相比,本发明的有益效果如下:
本发明选用沸点高、具有优良溶解性能、高的热稳定性和化学稳定性的离子液体1-丙基-3-甲基咪唑碘盐以及在有机溶剂中溶解度比较大的AgSPh为反应原料,在温和的条件下合成出簇基银碘化合物。本发明制备方法简单、条件温和、可重复性好、产率高,为无机合成与制备领域的发展注入新的活力。此外,本发明制备出的银碘化物具有热致荧光变色性能,可作为温度传感器应用。
附图说明
图1为本发明所述簇基银碘化合物的结构单元图;
图2为本发明所述簇基银碘化合物的空间结构图;
图3为本发明所述簇基银碘化合物的XRD图;
图4为本发明所述簇基银碘化合物在77 K时的荧光光谱图;
图5为本发明所述簇基银碘化合物的变温荧光图;
图6为本发明所述簇基银碘化合物的不同温度下的荧光色坐标图;
图7为本发明所述簇基银碘化合物的荧光强度温度传感拟合图。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚,下面结合附图和具体实施例对本发明的技术方案作出进一步的说明,但所述实施例旨在解释本发明,而不能理解为对本发明的限制,实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行,所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
实施例1
一种簇基银碘化合物的制备方法,具体为:
首先向硬质玻璃管中加入0.1 mmol AgSPh、0.3 mmol PrImI(上海成捷化学有限公司)、0.1 mmol Dabco(阿拉丁试剂公司),0.4 mL乙腈-水混合液(VCH3CN: VH2O= 3 : 1)(国药集团化学试剂有限公司),玻璃管的填充率为10 %,超声分散均匀,然后在酒精喷灯上封管(即把玻璃管封住,用以使反应在密闭状态下进行)。放入反应釜中,再于120℃的干燥箱(无需真空)中恒温放置150小时,待自然冷却至室温,观察到玻璃管内有浅黄色六边形片状晶体,用乙腈洗涤、干燥即得。
所得簇基银碘化合物的产率为68%,分子式为:[DabcoAg8I6(SPh)2]。扫描电镜光电子能谱(EDS)结果显示化合物中Ag: I: S为4 : 3 : 1;元素分析结果显示化合物中:C为11.06 %,H 为 1.14 %,N为1.43 %,均与结构分析的结果相符合
所得簇基银碘化合物的结构测定:
在显微镜下选取合适大小该簇基银碘化合物的单晶,室温下在Bruker APEX IICCD面探衍射仪上,用经石墨单色器单色化的射线(/>= 0.71073 Å),以/>方式收集衍射数据。所有衍射数据使用SADABS程序进行半经验吸收校正。晶胞参数用最小二乘法确定。数据还原和结构解析分别使用SAINT和SHELXTL程序完成。晶体结构用直接法解出,金属原子的位置通过直接法的E-map 确定,而其它非氢原子则利用差值傅立叶函数法和最小二乘法确定,然后进行各向异性精修。详细的所得化合物的晶体测定数据见表1。
结构如图1所示,所得化合物的结构属于三方晶系,空间群为P31m。晶体学数据如表1所示。XRD图如图3所示,实验样品谱图的特征峰与模拟谱图的特征峰相互对应,说明化合物的晶体为纯相。
表1 化合物[DabcoAg8I6(SPh)2]的晶体学数据
所述簇基银碘化合物属三方晶系,空间群为P31m,晶胞参数为:a= 15.6316 Å (3),b= 15.6316 Å (3) ,c= 12.0038Å (5) ,α=β=90.0°,γ=120°。
该簇基银碘化合物的结构是由Ag8I6(SPh)2层和线性的Dabco配体构建的三维“柱-层”杂化骨架。化合物的次级结构单元是一个Ag8I6十二面体簇(见图1),其中,八个Ag原子呈立方体排列,µ 4-I原子桥连同一个面上的四个Ag原子。所有的Ag原子都采用四面体配位的模式,可分为两类:6个Ag离子与3个µ 4-I原子和1个SPh-配体中的S原子配位,其余2个Ag+离子与3个µ 4-I原子和1个Dabco配体中的N原子配位。I原子都采用µ 4-I的连接模式。Ag…Ag之间存在弱的相互作用。每个Ag8I6簇和相邻的六个Ag8I6簇通过µ 3-S形成2D的Ag8I6(SPh)2层,相邻的Ag8I6(SPh)2层通过线性桥连配体Dabco扩展形成3D的杂化骨架(见图2)。如果把每个Ag8I6簇简化为六连接的节点,把µ 3-SPh看做三连接的节点,把Dabco看做线性连接体,那个该化合物的结构可以简化为(8,3)连接的tfz-d拓扑,Schläfli 符号为 (43)2(46·618·84)(Cryst. Growth Des.2013,13, 1618-1625)。
所得簇基银碘化合物,其粉末X-射线衍射图谱测定:
样品研磨均匀后,利用粉末X射线衍射仪测定化合物的粉末X-射线衍射数据,如图3所示,实验合成样品的衍射特征峰与单晶数据模拟的特征峰出峰位置一致,说明化合物的晶体为纯相。
所得簇基银碘化合物的荧光性质测定:
取适量样品,用FLS980稳瞬态荧光光谱仪测定其发光性质。在室温时该化合物的荧光不明显,但是在77 K时,当以350 nm的紫外光激发时,化合物表现出荧光双发射性质,最大发射峰分别位于597 (HE发射)和787nm (LE发射)处,如图4所示,发光颜色为橘红色。
所得簇基银碘化合物的变温荧光测定:
取适量样品,用FLS980荧光光谱仪测定其变温发光性质,结果显示(见图5):以350nm的紫外光激发,80 K时最大发射峰分别位于597 nm和787处,发光颜色为橘红色。随着温度从80 K升到260 K,位于597 nm和787处的发射峰没有发生明显的位移,两个发射峰的强度显著降低,280 K时发光淬灭,且两个发射峰之间没有明显的共振现象。随着温度从80K上升到260K时,其发光颜色由橘红色逐渐变橘黄色,具有显著的热致荧光变色行为,图6为该化合物在不同温度下的荧光色坐标图。
实施例2
一种簇基银碘化合物的制备方法,具体为:
首先向硬质玻璃管中加入0.1 mmol AgSPh、0.3 mmol PrImI(上海成捷化学有限公司)、0.15 mmol Dabco(阿拉丁试剂公司),0.4 mL乙腈-水混合液(VCH3CN: VH2O= 3 : 1)(国药集团化学试剂有限公司),玻璃管的填充率为10 %,超声分散均匀,然后在酒精喷灯上封管(即把玻璃管封住,用以使反应在密闭状态下进行)。放入反应釜中,再于120℃的干燥箱(无需真空)中恒温放置150小时,待自然冷却至室温,观察到玻璃管内有浅黄色六边形片状晶体,用乙腈洗涤、干燥即得。
实施例3
一种簇基银碘化合物的制备方法,具体为:
首先向硬质玻璃管中加入0.1 mmol AgSPh、0.3 mmol PrImI(上海成捷化学有限公司)、0.23 mmol Dabco(阿拉丁试剂公司),0.4 mL乙腈-水混合液(VCH3CN: VH2O= 3 : 1)(国药集团化学试剂有限公司),玻璃管的填充率为10 %,超声分散均匀,然后在酒精喷灯上封管(即把玻璃管封住,用以使反应在密闭状态下进行)。放入反应釜中,再于120℃的干燥箱(无需真空)中恒温放置150小时,待自然冷却至室温,观察到玻璃管内有浅黄色六边形片状晶体,用乙腈洗涤、干燥即得。
实施例4
一种簇基银碘化合物的制备方法,具体为:
首先向硬质玻璃管中加入0.1 mmol AgSPh、0.3 mmol PrImI(上海成捷化学有限公司)、0.27 mmol Dabco(阿拉丁试剂公司),0.4 mL乙腈-水混合液(VCH3CN: VH2O= 3 : 1)(国药集团化学试剂有限公司),玻璃管的填充率为10 %,超声分散均匀,然后在酒精喷灯上封管(即把玻璃管封住,用以使反应在密闭状态下进行)。放入反应釜中,再于120℃的干燥箱(无需真空)中恒温放置150小时,待自然冷却至室温,观察到玻璃管内有浅黄色六边形片状晶体,用乙腈洗涤、干燥即得。
实施例5
一种簇基银碘化合物的制备方法,具体为:
首先向硬质玻璃管中加入0.1 mmol AgSPh、0.3 mmol PrImI(上海成捷化学有限公司)、0.25 mmol Dabco(阿拉丁试剂公司),0.4 mL乙腈-水混合液(VCH3CN: VH2O= 3 : 1)(国药集团化学试剂有限公司),玻璃管的填充率为10 %,超声分散均匀,然后在酒精喷灯上封管(即把玻璃管封住,用以使反应在密闭状态下进行)。放入反应釜中,再于120℃的干燥箱(无需真空)中恒温放置150小时,待自然冷却至室温,观察到玻璃管内有浅黄色六边形片状晶体,用乙腈洗涤、干燥即得。
应用试验
将本发明实施例1所得簇基银碘化合物(即下述样品)作为发光材料进行温度传感研究:
利用荧光光谱仪对化合物的变温荧光行为进行了研究。研究结果显示:化合物在不同的温度下对温度的响应明显不同,随着温度从80 K升到260 K,位于597 nm和787处的发射峰没有发生明显的位移,发射峰的强度显著降低,280 K时发光淬灭,其发光颜色由橘红色逐渐变为橘黄色,具有显著的热致荧光变色行为。值得注意的是,随着温度的升高,LE和HE发射是独立的,并且是同步衰减的,在两个不同的温度范围内(80-260 K以及80-200K),发射强度与温度之间存在良好的线性关系(线性相关系数为分别为0.99448和09814),说明所得簇基银碘化合物是一种灵敏的强度型温度传感材料,可作为荧光变色温度传感器应用于荧光温度传感领域。本发明为新型温度传感器的研发提供了新思路。
最后所应说明的是:上述实施例仅用于说明而非限制本发明的技术方案,任何对本发明进行的等同替换及不脱离本发明精神和范围的修改或局部替换,其均应涵盖在本发明权利要求保护的范围之内。
Claims (6)
1.一种簇基银碘化合物,其特征在于,化学式为[DabcoAg8I6(SPh)2],其中,Dabco为三乙烯二胺,SPh-为苯硫酚阳离子;
所述簇基银碘化合物的晶体属三方晶系,空间群为 P31m,晶胞参数为:a = 15.6316 Å(3) , b = 15.6316 Å (3) , c = 12.0038Å (5) ,α = β = 90.0°,γ =120°。
2.权利要求1所述的簇基银碘化合物的制备方法,其特征在于,将苯硫酚银、三乙烯二胺、1-丙基-3-甲基咪唑碘盐和溶剂混合均匀,然后于60-120℃恒温反应120-180小时,反应结束后产物经洗涤、干燥即得。
3.根据权利要求2所述簇基银碘化合物的制备方法,其特征在于,所述苯硫酚银、1-丙基-3-甲基咪唑碘盐、三乙烯二胺的摩尔比为1:2.5-4.0: 1.0-2.7。
4.根据权利要求2所述簇基银碘化合物的制备方法,其特征在于,所述溶剂为体积比2-4 : 1的乙腈-水混合液。
5.权利要求1所述簇基银碘化合物作为荧光材料的应用。
6.权利要求1所述簇基银碘化合物作为荧光温度传感器的应用。
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