Coordination Polymers from 2-Chloroterephthalate Linkers: Synthesis, Structural Diversity, and Catalytic CO2 Fixation

Author(s)

Gu, Jinzhong ^{[1, 2]} ; Wan, Shimao ^{[1, 2]} ; Cheng, Xiaoyan ^{[1, 2]} ; Kirillova, V, Marina ; Kirillov, Alexander M. ^{[3, 4]}

Affiliation

^[1] Lanzhou Univ, State Key Lab Appl Organ Chem, Key Lab Nonferrous Met Chem & Resources Utilizat, Lanzhou 730000 - Peoples R China

^[2] Lanzhou Univ, Coll Chem & Chem Engn, Lanzhou 730000 - Peoples R China

^[3] Kirillova, Marina, V, Univ Lisbon, Ctr Quim Estrutural, Inst Super Tecn, P-1049001 Lisbon - Portugal

^[4] Peoples Friendship Univ Russia, Res Inst Chem, RUDN Univ, Moscow 117198 - Russia

• Document type: Journal article
• Source: Crystal Growth & Design; v. 21, n. 5, p. 2876-2888, MAY 5 2021.
• Web of Science Citations: 0

Abstract

In contrast to the broad use of terephthalic acid as a building block for generating metal-organic architectures, functionalized terephthalate ligands remain significantly less investigated. In the present study, 2-chloroterephthalic acid (CltaH(2)) was used as an unexplored linker for assembling a new series of metal(II) coordination polymers (CPs) formulated as [{[}Cu-2(mu-Clta)(mu(4)-Clta)(bipy)(2)]center dot 2H(2)O](n) (1), [{[}Cu-2(mu-Clta)(mu(4)-Clta)(phen)(2)]center dot 2H(2)O](n) (2), {[}Co-3(mu(4)-Clta)(3)(phen)(2)](n) (3), [{[}Zn-4(mu(3)-Clta)(2)(mu(4)-Clta)(mu(3)-OH)(2)(phen)(2)]center dot 2H(2)O](n) (4), [{[}Cd(mu(3)-Clta)(phen)]center dot H2O](n) (5), {[}Co-2( mu-Clta)(mu(4)-Clta)(mu-bpa)(2)](n) (6), {[}Zn-2(mu(4)-Clta)(mu(4)-biim)](n) (7), and {[}Cd(mu-Clta)(H(2)biim)(2)](n) (8). These compounds were prepared hydrothermally from the respective metal(II) chlorides, CltaH(2), and different N-donor supporting ligands acting as mediators of crystallization (i.e., bipy, 2,2'-bipyridine; phen, 1,10-phenanthroline; bpa, bis(4-pyridyl)amine; H(2)biim, 2,2'-biimidazole). The structures of the coordination polymers 1-8 range from one-dimensional chains (5 and 8) and two-dimensional layers (1-3) to three-dimensional (3D) frameworks (4, 6, and 7); the latter also include 3D + 3D interpenetrated examples (4, 6). Apart from different dimensionalities, the compounds also feature distinct topologies, namely, 3,4L13 in 1 and 2, 3,4,6L12 in 3, pcu in 4, SP 1-periodic net (4,4)(0,2) in 5, sqc65 in 6, 2C1 in 8, and a new kir1 topology in 7. Given the similarity of the reaction conditions, the obtained wide diversity of structures is primarily determined by the type of metal(II) node and/or crystallization mediator. All the CPs were also screened as heterogeneous catalysts in a model CO2 fixation reaction, namely, in the coupling of epoxide (epichlorohydrin) with carbon dioxide, under atmospheric pressure, and in the absence of added solvent, to produce the corresponding cyclic carbonate. The catalytic reactions were optimized for CP 4, which revealed the best activity (up to 71% product yields), good stability, and recyclability for up to four reaction steps. Finally, CPs 3-8 are the first examples of cobalt, zinc, and cadmium coordination compounds assembled from 2-chloroterephthalic acid, thus widening its very limited application in the design of functional metal-organic architectures. (AU)

• FAPESP's process: 18/01258-5 - Novel chemical catalytic and photocatalytic processes for the direct conversion of methane and CO2 to products
• Grantee: José Maria Correa Bueno
• Support Opportunities: Research Projects - Thematic Grants