【大学化学】doi: 10.12461/PKU.DXHX202511107
笔者在大学入学之初就受教于华彤文老师,后来跟随华老师做研究、搞教学、写教材,直至担任《大学化学》主编时依然听取华老师的教诲。在此文中分享40余年来近距离观察、感受和学习华老师严谨治学、勇于担当的教学与研究的态度和方法,期待我国的化学教育教学事业薪火相传,持续发展。
【大学化学】doi: 10.12461/PKU.DXHX202405208
将本科课程中的脑文格反应等有机化学内容与有机太阳能电池研究前沿紧密结合,通过实验让学生深入了解有机化学课程中的化学反应。该实验利用脑文格反应合成了一个宽带隙的稠环电子受体材料A831,通过对实验数据进行分析,确定材料是通过削弱端基的拉电子能力,提升了材料的最低未占有分子轨道(LUMO)能级,进而获得高电压的有机太阳能电池。该实验充分培养了学生运用基础知识解决科研问题的能力,体现了“基础知识–实际应用”的有机实验教学模式,适合作为面向高年级本科生的综合实验教学课程。
【大学化学】doi: 10.3866/PKU.DXHX202302060
ShelXle是一款用于小分子晶体结构精修的专业性可视化软件,在高校群体中拥有相当数量的用户,但目前国内外有关该软件使用研究的文献报道非常少,导致众多师生在精修过程中碰到问题时不知道如何进行应对。本文详细介绍了ShelXle的开发背景、基本功能、特色功能及操作方法,结合若干案例,通过与其他软件对比,分析了ShelXle在小分子晶体结构精修中所具备的技术优势,并就如何利用ShelXle提升精修效果提出了一些参考性建议。
【无机化学学报】doi: 10.11862/CJIC.20250080
以1,1′-二甲基-4,4′-联吡啶(甲基紫精,MV)二氯化物和Keggin型多酸单元合成的晶态材料(MV)2[HPWⅤ2WⅥ10O40]·2H2O为催化剂,在无有机溶剂、室温条件下合成了一系列β-氨基醇类化合物。该催化剂不仅能够高效催化β-氨基醇的合成,而且具有良好的稳定性及可回收性。经过6次循环使用后,催化剂活性未出现明显下降,表明其具有较好的循环利用潜力。与传统方法相比,该反应体系不使用有机溶剂并具有反应条件温和、操作简单、环境友好等优点。
【大学化学】doi: 10.12461/PKU.DXHX202504038
X射线单晶结构分析是确定结构的重要手段,传统结构精修基于独立原子模型,忽略了化学键中的非球形电子分布,导致了氢原子位置的较大误差。利用非球形原子模型,不仅可以提升晶体结构精修结果,而且能够精准确定氢原子位置。本文介绍了非球形结构精修方法,以Olex2平台集成的非球形原子精修工具NoSpherA2为例,用一个共晶分子作为案例演示,展示了该方法在提升晶体结构解析精度方面的优势。通过本文的学习,化学专业学生和晶体学研究者能够掌握非球形结构精修方法,拓展量子晶体学的研究前沿知识。
【无机化学学报】doi: 10.11862/CJIC.20240066
Two new viologen-polyoxometalate hybrid crystalline materials: (MV)2[HPW2ⅤW10ⅥO40] ·2H2O (1) and (EV)2[Mo8O26] (2) have been synthesized by using the cations of 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (methyl viologen, MV) and 1, 1'-diethyl-4, 4'-bipyridinium dibromide (ethyl viologen, EV) as the electron acceptors, and the electron-rich polyoxometalate anions as the electron donors. The structures of compounds 1 and 2 have been determined by single-crystal X-ray crystallography. Hydrogen bond interactions exist between the cations and the anions in 1 and 2. Interestingly, 2 has a photochromic performance with a light response time within 1 min. The photochromic mechanism of compound 2 has been investigated by solid-state diffuse reflection, electron paramagnetic resonance and theoretical calculation. 1 and 2 show good catalytic performance in the photocatalytic degradation of several organic dyes (methylene blue, pararosaniline hydrochloride and rhodamine 6G).
【无机化学学报】doi: 10.11862/CJIC.20240376
Under the condition of solvothermal synthesis, the viologen ligand 1, 1′‐bis(3‐carboxyphenyl)‐(4, 4′‐bipyri‐ dine) dichloride (H2bcbpy·2Cl) and KI are coordinated with the metal cadmium ions. A case of thermochromic coor‐ dination polymer [Cd(bcbpy)I2] ·2H2O (1) was constructed. Complex 1 displays a 1D chain structure and exhibits thermochromic behavior. Under different temperature stimulation, the complex (ground) slowly changed from green to yellow‐green, and with the increase of temperature, the color of complex 1 gradually deepened, and finally became orange‐yellow. Therefore, complex 1 was prepared as a thermochromic film. In addition, we also performed electrochemical tests on complex 1, which showed that the complex is a semiconductor material.
【无机化学学报】doi: 10.11862/CJIC.20250325
A novel viologen-based photochromic coordination polymer, namely [Zn(CV)0.5(BDC)(H2O)]·2H2O (1), has been successfully constructed via solvothermal self-assembly of Zn2+ ions with the 1, 1′-bis(2-carboxyethyl)-4, 4′-bipyridinium ((H2CV)2+) as a photo-responsive functional unit and terephthalic acid (H2BDC) as an auxiliary bridging ligand. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 1D chain-like framework. Upon light irradiation, complex 1 exhibited a distinct photo-responsive color-changing behavior, transforming from colorless to blue. The blue-colored sample gradually faded and reverted to its original colorless state upon being placed in a dark environment at room temperature, demonstrating excellent reversible photochromic properties. On the basis of its photochromic performance, the application of this complex in ink-free printing has been explored. Furthermore, complex 1 emitted blue light under UV irradiation in a dark environment, revealing favorable photoluminescent characteristics. In addition, complex 1 possessed multiple photoswitchable properties.
【无机化学学报】doi: 10.11862/CJIC.20250205
通过溶剂热法将1,1′-二甲基-4,4′-联吡啶阳离子(甲基紫精阳离子,MV2+)和1,1′-二乙基-4,4′-联吡啶阳离子(乙基紫精阳离子,EV2+)引入金属有机框架Zn-NH2-BDC中,得到2种紫精修饰的金属有机框架{(MV)[Zn2(NH2-BDC)3]}n (1)、{(EV)[Zn3(NH2-BDC)4]}n (2)(NH2-H2BDC=2-氨基对苯二甲酸)。2个配合物展现出良好的催化性能,在温和反应条件下,能够高效、稳定地一锅法催化Knoevenagel缩合-Michael加成环化反应,生成4H-吡喃衍生物,产率均达到98%以上。在回收利用方面,2种材料可重复使用至少5次,并保持其原有催化活性。
【大学化学】doi: 10.12461/PKU.DXHX202406090
过渡金属催化的碳-杂原子偶联反应是有机合成化学中一个重要的研究方向。Kharasch-Sosnovsky反应利用过氧苯甲酸叔丁酯作为氧化剂,在金属铜催化的条件下,将烯烃转化为烯丙酯类化合物,完成碳氧键构筑。响应国家“双碳”战略,开发新的催化体系,实现含碳物质的绿色高效转化已经成为有机化学家们追求的重要目标。基于此,Kharasch-Sosnovsky反应在不对称反应、配体设计、底物范围扩展以及环境友好性方面取得了显著的改进。本文简要介绍了Kharasch-Sosnovsky反应的发现与新的研究进展,结合前沿科研成果,不仅有助于加深学生对基础有机化学中相关内容的理解,同时可以有效补充现有教材中的知识空缺,实现基础化学知识与学科前沿研究的深度融合。
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