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使用基于吡啶-2,3-二羧酸酯的金属有机框架进行催化C-H键活化和Knoevenagel缩合反应

Catalytic C-H Bond Activation and Knoevenagel Condensation Using Pyridine-2,3-Dicarboxylate-Based Metal-Organic Frameworks.

作者信息

Pandey Rampal, Singh Durgesh, Thakur Neha, Raj Krishna K

机构信息

Department of Chemistry, National Institute of Technology Uttarakhand, Srinagar, Uttarakhand 246174, India.

Department of Chemistry, Dr. Harisingh Gour University, Sagar, Madhya Pradesh 470003, India.

出版信息

ACS Omega. 2021 May 12;6(20):13240-13259. doi: 10.1021/acsomega.1c01155. eCollection 2021 May 25.

Abstract

Three 1D coordination polymers (CPs) [M(pdca)(HO)] (M = Zn, Cd, and Co; ), and a 3D coordination framework {[(CH)NH][CuK(2,3-pdca)(pa)(NO)]} () (2,3-pdca = pyridine-2,3-dicarboxylate and pa = picolinic acid), have been synthesized adopting a solvothermal reaction strategy. The CPs have been thoroughly characterized using various spectral techniques, that is, elemental analyses, FT-IR, TGA, DSC, UV/vis, and luminescence. Structural information on was obtained by PXRD and X-ray single-crystal analyses, whereas morphological insights were attained through FESEM, AFM, EDX, HRTEM, and BET surface area analyses. Roughness parameters were calculated from AFM analysis, whereas dimensions of small domains and interplanar spacing were defined with the aid of HRTEM. CPs are 1D isostructural networks, whereas is a 3D framework. Moreover, display moderate luminescence at rt. In addition, have been applied as economic and efficient porous catalysts for the Knoevenagel condensation reaction and C-H bond activation under mild conditions with good yields (95-98 and 97-99%), respectively. Notably, can be reused up to seven cycles, whereas can be reused up to five catalytic cycles with retained catalytic efficiency. Relative catalytic efficacy toward the Knoevenagel condensation reaction follows in the order > > > , whereas > > > for C-H activation. The present result demonstrates synthetic, structural, optical, morphological, and catalytic aspects of .

摘要

采用溶剂热反应策略合成了三种一维配位聚合物(CPs)[M(pdca)(HO)] (M = Zn、Cd和Co; )以及一种三维配位框架{[(CH)NH][CuK(2,3 - pdca)(pa)(NO)]} ( )(2,3 - pdca = 吡啶 - 2,3 - 二羧酸酯,pa = 吡啶甲酸)。使用各种光谱技术对这些CPs进行了全面表征,即元素分析、傅里叶变换红外光谱(FT - IR)、热重分析(TGA)、差示扫描量热法(DSC)、紫外/可见光谱(UV/vis)和发光光谱。通过粉末X射线衍射(PXRD)和X射线单晶分析获得了 的结构信息,而通过场发射扫描电子显微镜(FESEM)、原子力显微镜(AFM)、能量散射X射线光谱(EDX)、高分辨率透射电子显微镜(HRTEM)和比表面积(BET)分析获得了形态学见解。粗糙度参数由AFM分析计算得出,而小区域尺寸和晶面间距借助HRTEM确定。CPs 是一维同构网络,而 是三维框架。此外, 在室温下显示出适度的发光。此外, 已被用作经济高效的多孔催化剂,分别在温和条件下用于Knoevenagel缩合反应和C - H键活化,产率良好(分别为95 - 98%和97 - 99%)。值得注意的是, 最多可重复使用7个循环,而 最多可重复使用5个催化循环且保持催化效率。对Knoevenagel缩合反应的相对催化效率顺序为 > > > ,而对于C - H活化则为 > > > 。目前的结果展示了 的合成、结构、光学、形态和催化方面。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b4c9/8158822/34e55affc451/ao1c01155_0011.jpg

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