Synthesis and crystal structures of two tri- and tetra-heterometallic Ni(ii)–Mn(ii)/Ni(ii)–Co(iii) complexes from two different Ni(ii)-containing metalloligands: effective catalytic oxidase activity and Schottky device approach. (25th October 2022)

• Record Type: Journal Article
• Authors: Das, Manik; Das, Mainak; Ray, Subham; Das, Uttam Kumar; Laha, Soumik; Ray, Partha Pratim; Samanta, Bidhan Chandra; Maity, Tithi
• Is Part Of: New journal of chemistry. Volume 46:Number 44(2022)
• Page Start: 21103
• Page End: 21114
• Publication Date: 2022-10-25
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d2nj03535a
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The development of tri- and tetra-nuclear heterometallic Ni(ii )–Mn(ii )/Ni(ii )–Co(iii ) complexes with effective catalytic oxidase activity and the Schottky device approach. Abstract : Using two different metalloligands [NiLA] and [NiLB], developed using two different N2 O2 donor Schiff bases, H2 LA 6, 6′-((1 E, 1′ E )-((2, 2-dimethylpropane-1, 3-diyl)bis(azaneylylidene))bis(2-methoxyphenol) and H2 LB 6, 6′-((1 E, 1′ E )-((2, 2 (2-ethoxyphenol), two new tetra- and trinuclear heterometallic complexes, [(NiLA)2 (CH3 COO)2 (SCN)2 (Co)2 ] (complex 1 ) and [(NiLB)2 (SCN)2 Mn] (complex 2 ), have been synthesized. The two newly formed complexes have primarily been characterized using several spectroscopic techniques. According to the single-crystal structural study, the metalloligand portion is shared by both crystals. Complex 1 is a tetranuclear complex where Ni(ii ) is connected to Co(ii ) via acetate and phenoxide bridging, whereas complex 2 is a trinuclear complex where each Ni(ii ) center is coordinated to Mn(ii ) via phenoxide bridging only. It is interesting to note that the thiocyanate moiety in complex 1 is linked to Co(ii ), whereas in complex 2, it is linked to Ni(ii ) as a secondary anionic residue. Following structural analysis, both complexes were exposed to catecholase-like activity to test their ability to aerially oxidize 3, 5-di- tert -butylcatechol. The calculated turnover numbers ( K cat ) 355 h −1 and 286 h −1 for complexes 1 and 2, respectively, unveiled that complex 1 is more susceptible to this catalytic process. The generation of Ni(i ) in complex 1 is more favorable than the formation of Mn(i ) in complex 2 during catalysis and this is the factor responsible for the higher susceptibility of complex 1 towards the catalytic process. To determine whether both the studied complexes can function as effective Schottky devices, the band gap values for complexes 1 and 2 were used to calculate the diode parameters. The results show that complex 1 will function as a better Schottky device than the complex 2 .