Synthesis and application of [Zr-UiO-66-PDC-SO3H]Cl MOFs to the preparation of dicyanomethylene pyridines via chemical and electrochemical methods

Amir Mohammad Naseri; Mahmoud Zarei; Saber Alizadeh; Saeed Babaee; Mohammad Ali Zolfigol; Davood Nematollahi; Jalal Arjomandi; Hu Shi

doi:10.1038/s41598-021-96001-7

Synthesis and application of [Zr-UiO-66-PDC-SO₃H]Cl MOFs to the preparation of dicyanomethylene pyridines via chemical and electrochemical methods

Sci Rep. 2021 Aug 19;11(1):16817. doi: 10.1038/s41598-021-96001-7.

Authors

Amir Mohammad Naseri¹, Mahmoud Zarei², Saber Alizadeh³, Saeed Babaee¹, Mohammad Ali Zolfigol⁴, Davood Nematollahi⁵, Jalal Arjomandi¹, Hu Shi⁶

Affiliations

¹ Faculty of Chemistry, Bu-Ali-Sina University, 65174-38683, Hamedan, Iran.
² Faculty of Chemistry, Bu-Ali-Sina University, 65174-38683, Hamedan, Iran. mahmoud8103@yahoo.com.
³ Faculty of Chemistry, Bu-Ali-Sina University, 65174-38683, Hamedan, Iran. s.alizade66@yahoo.com.
⁴ Faculty of Chemistry, Bu-Ali-Sina University, 65174-38683, Hamedan, Iran. zolfi@basu.ac.ir.
⁵ Faculty of Chemistry, Bu-Ali-Sina University, 65174-38683, Hamedan, Iran. nemat@basu.ac.ir.
⁶ School of Chemistry and Chemical Engineering, Institute of Molecular Science, Shanxi University, Taiyuan, 030006, China.

Abstract

A metal-organic framework (MOF) with sulfonic acid tags as a novel mesoporous catalyst was synthesized. The precursor of Zr-UiO-66-PDC was synthesized both via chemical and electrochemical methods. Then, zirconium-based mesoporous metal-organic framework [Zr-UiO-66-PDC-SO₃H]Cl was prepared by reaction of Zr-UiO-66-PDC and SO₃HCl. The structure of [Zr-UiO-66-PDC-SO₃H]Cl was confirmed by FT-IR, PXRD, FE-SEM, TEM, BET, EDX, and Mapping analysis. This mesoporous [Zr-UiO-66-PDC-SO₃H]Cl was successfully applied for the synthesis of dicyanomethylene pyridine derivatives via condensation of various aldehyde, 2-aminoprop-1-ene-1,1,3-tricarbonitrile and malononitrile. At the electrochemical section, a green electrochemical method has successfully employed for rapid synthesis of the zirconium-based mesoporous metal-organic framework UiO-66-PDC at room temperature and atmospheric pressure. The synthesized UiO-66-PDC has a uniform cauliflower-like structure with a 13.5 nm mean pore diameter and 1081.6 m² g^-1 surface area. The described catalyst [Zr-UiO-66-PDC-SO₃H]Cl was also employed for the convergent paired electrochemical synthesis of dihydropyridine derivatives as an environmentally friendly technique under constant current at 1.0 mA cm^-2 in an undivided cell. The proposed method proceeds with moderate to good yields for the model via a cooperative vinylogous anomeric based oxidation.