| 硫酸镉无机层和原位反应生成的吡啶基四氮唑有机配体构筑的两个层-柱状三维无机-有机杂化材料:合成和表征 |
| Syntheses and Characterization of Two Three-Dimensional Layered-Pillared Inorganic-Organic Hybrid Materials Constructed from Inorganic Cadmium Sulfate Layers and in situ Generated Organic 5-(Pyridyl)tetrazolate Ligands |
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| 摘要: 以硫酸镉、叠氮化钠和4-氰基吡啶或3-氰基吡啶为反应物,在水热条件下,通过原位反应分别得到了2个基于硫酸根离子和5-(4-吡啶基)四氮唑(4-Hptz)或5-(3-吡啶基)四氮唑(3-Hptz)配体的,具有三维层-柱状框架结构的无机-有机杂化材料,即[Cd2(H2O)(OH)(SO4)(4-ptz)]n(1)和[Cd2(OH)(SO4)(3-ptz)]n(2)。通过元素分析、红外光谱、热重分析以及单晶和粉末X-射线衍射分析对它们的组成和结构进行了表征。在配合物1和2的结构中,每个镉(Ⅱ)离子的配位数均为6,处于扭曲的八面体配位环境中,SO42-和OH-阴离子连接镉(Ⅱ)离子扩展形成碱式硫酸镉的二维无机阳离子层结构[Cd2(H2O)(OH)(SO4)]nn+(1)或[Cd2(OH)(SO4)]nn+(2),相邻的二维无机阳离子层间再通过4-ptz-(1)或3-ptz-(2)进一步柱连接,形成三维层-柱状结构的无机-有机杂化框架结构。室温下的固体荧光实验表明,在350nm的光激发下,配合物1和2分别在481和489nm处出现强烈的荧光发射。 |
| 关键词: 无机-有机杂化材料 5-(吡啶基)四氮唑 混合配体 晶体结构 荧光 |
| 基金项目: 国家自然科学基金资助项目(No.21071099,21363001)和广东省普通高校特色创新(自然科学类)项目(No.2014KTSCX169)。 |
| Abstract: Hydrothermal reactions of CdSO4 and NaN3 with 4-cyanopyridine or 3-cyanopyridine yielded two three-dimensional layered-pillared inorganic-organic hybrid materials based on mixed ligands of sulfate and in situ synthesized 5-(4-pyridyl)tetrazolate(4-ptz-) or 5-(3-pyridyl)tetrazolate(3-ptz-), respectively, namely, [Cd2(H2O)(OH)(SO4)(4-ptz)]n (1) and [Cd2(OH)(SO4)(3-ptz)]n (2), which have been structurally characterized by elemental analysis (EA), infrared spectroscopy (IR), thermogravimetric analysis (TGA), single-crystal and powder X-ray diffraction. In 1 and 2, each Cd(Ⅱ) ion is six-coordinated with a distorted octahedral coordination geometry, which are connected through SO42- and OH-, leading to an infinite two-dimensional cation layer structure of [Cd2(H2O)(OH)(SO4)]nn+(1) or [Cd2(OH)(SO4)]nn+(2). These adjacent two-dimensional cation layers are further linked by 4-ptz- (1) or 3-ptz- (2) pillared ligands to form infinite three-dimensional layered-pillared inorganic-organic hybrid frameworks architecture of 1 and 2, respectively. In addition, the results of photoluminescent measurements in the solid state at room temperature indicate that 1 and 2 all exhibit intense fluorescent emissions at λmax=481 nm and 489 nm when excited at 350 nm, respectively. |
| Keywords: organic-inorganic hybrid materials 5-(pyridyl)tetrazole mixed-ligand crystal structure fluorescence |
| 投稿时间：2014-02-01 修订日期：2015-03-18 |
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| 钟地长,卢文贯.硫酸镉无机层和原位反应生成的吡啶基四氮唑有机配体构筑的两个层-柱状三维无机-有机杂化材料:合成和表征[J].无机化学学报,2015,31(6):1177-1184. |
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