新型锗中心多孔芳香材料的设计合成和表征  

Designed Synthesis and Characterization of Novel Germanium Centered Porous Aromatic Frameworks(Ge-PAFs)

作　　者：元野[1] 闫卓君[1] 任浩[1] 刘青英[1] 朱广山[1] 孙福兴[1] 

机构地区：[1]吉林大学无机合成与制备化学国家重点实验室,长春130012

出　　处：《化学学报》2012年第13期1446-1450,共5页Acta Chimica Sinica

基　　金：国家重点基础研究发展计划(973计划;No.2012CB821700);重大国际(地区)合作研究项目(No.21120102034);国家自然科学基金(No.20831002)资助~~

摘　　要：采用四(4-溴苯基)锗烷作为基块,以1,4-苯二硼酸和4,4'-联苯基二硼酸作为桥联,合成了两种锗中心的多孔芳香材料(Ge-PAFs).通过FTIR,MAS NMR,TGA,PXRD,SEM,TEM及N2吸附对该化合物的结构及性质进行表征.Ge-PAF-1和Ge-PAF-2具有优良的热稳定性(420℃失重5%)及化学稳定性.另外,该材料成功地在聚合物中引入锗元素为其在半导体等方面的应用提供了可能[1].A novel series of germanium centered porous aromatic frameworks （Ge-PAFs） based on tetrakis（4-bromophenyl）germane as building units and 1,4-benzenediboronic acid or 4,4＇-biphenyldiboronic acid as linkers were synthesized. These materials were characterized by Fourier transform infrared spectroscopy （FT-IR）, 13C solid-state NMR, thermogravimetric analysis （TGA）, powder X-ray diffraction （PXRD）, scanning electron microscopy （SEM）, high-resolution transmission electron microscopy （TEM）, and N2 gas sorption. FTIR spectroscopy is useful in probing the structure of Ge-PAFs networks. From the disappearance of the intense B--OH bands （at 3370 cm^-1） and the C--Br bands （at 482 cm^-1） in the FT-IR spectra, the formation of the product can be preliminarily confirmed. The solid-state 13C CP/MAS NMR spectra of Ge-PAFs indicate that a group of signals with a chemical shift in the range of J 120--145 could be observed. They are related to aromatic carbon atoms in the framework-building phenylene groups. Both the FTIR and 13C CP/MAS NMR analyses show no obvious signals assigned to the halogen or boronic acid end groups, testifying that an almost com- plete coupling reaction has taken place. PXRD was carried out to investigate the crystallinity of Ge-PAFs, which indicate the amorphous texture. No long-range frameworks could be due to distortion and interpenetration of the phenyl rings. SEM im- ages showed that Ge-PAF-1 and Ge-PAF-2 afforded a spherical morphology. Simultaneously, TEM revealed that both of Ge-PAFs possess a worm-like texture. The thermal stability of Ge-PAF-1 and Ge-PAF-2 was analyzed by TG analysis under air. These materials were stable up to 420 ℃ in air corresponding to 5% weight loss, which suggest that the Ge-PAFs exhibit high thermal stability. Moreover, Ge-PAF-1 and Ge-PAF-2 also show high chemical stability. It is also insoluble in common organic solvents such as methanol, ethanol, acetone, THF, CHC13 and DMF. The N2 sorption isotherms were measured at 77 K to chara

关 键 词：SUZUKI偶联反应 锗中心 多孔芳香材料 热稳定性 化学稳定性 

分 类 号：O621.2[理学—有机化学]