Synthesis and structural characterization of a new family of amino acid-based coordination complexes, and study of their potential application as nitrite reductases biomimetic electrocatalysts

JUAN MANUEL REY; FEDERICO MOVILLA; SEBASTIÁN SUÁREZ; FLORENCIA DI SALVO

Congreso; ACS - SPRING MEETING; 2021

Metalloproteins involved in oxidation-reduction process in metabolismare fundamental for the wellbeing of every organism. The use of amino acid-based compounds as ligands for theconstruction of biomimetic coordination systems, represents a promisingalternative for the development of new catalysts. The presence of N- andO-donor functional groups and their relative position, allows them to act aschelating agents. Herein, we study the synthesis, characterization, andproperties of a new family of copper, zinc and nickel coordination compoundsbased on ligands obtained from the aldehyde piperonal and the amino acidsL-Alanine (L1) and L-Phenylalanine (L2). The structures of the complexes areconfirmed on the basis of single crystal X-ray diffraction studies,spectroscopic and electrochemical characterization. It is found that the structuraldiversity depends on the metal center and ligand identity and bulkiness (Figure1). The inter and intra-molecular interactions between the ligands, mainly π-stacking and hydrogen bonds, aredeterminant for the formation of the complexes, and allow the stabilizationof geometrically distorted structures. Hence, Hirshfield surface analysis and topologicalstudies are performed to analyze the supramolecular chemistry. In addition, theuse of the Cu(II) complexes as potential candidates of nitrite reductasesmimics for electrocatalytic reduction of nitrite to NO are also explored usingexperimental studies and DFT calculations.@font-face{font-family:"Cambria Math";panose-1:2 4 5 3 5 4 6 3 2 4;mso-font-charset:0;mso-generic-font-family:roman;mso-font-pitch:variable;mso-font-signature:-536870145 1107305727 0 0 415 0;}@font-face{font-family:Calibri;panose-1:2 15 5 2 2 2 4 3 2 4;mso-font-charset:0;mso-generic-font-family:swiss;mso-font-pitch:variable;mso-font-signature:-536859905 -1073732485 9 0 511 0;}p.MsoNormal, li.MsoNormal, div.MsoNormal{mso-style-unhide:no;mso-style-qformat:yes;mso-style-parent:"";margin:0cm;mso-pagination:widow-orphan;font-size:12.0pt;font-family:"Times New Roman",serif;mso-fareast-font-family:"Times New Roman";mso-fareast-language:ES-TRAD;}.MsoChpDefault{mso-style-type:export-only;mso-default-props:yes;font-family:"Cambria",serif;mso-ascii-font-family:Cambria;mso-ascii-theme-font:minor-latin;mso-fareast-font-family:"MS Mincho";mso-fareast-theme-font:minor-fareast;mso-hansi-font-family:Cambria;mso-hansi-theme-font:minor-latin;mso-bidi-font-family:"Times New Roman";mso-bidi-theme-font:minor-bidi;mso-ansi-language:ES-TRAD;mso-fareast-language:ES;}div.WordSection1{page:WordSection1;}