Achieving multilevel conduction in a cost-effective transition metal complex of a redox-active ligand will be an efficient way for designing a molecular memristor.This study presents a rare example of a tris-azo anion...Achieving multilevel conduction in a cost-effective transition metal complex of a redox-active ligand will be an efficient way for designing a molecular memristor.This study presents a rare example of a tris-azo anion radical ligand-wrapped singlet five-coordinate low-spin Co(Ⅱ)complex,[(L)^(·−)Co(Ⅱ)]PF_(6),[1]PF_(6),that showed solution-processible resistive switching memory with synaptic functionality.The single-crystal X-ray structure,variable-temperature magnetic studies,and DFT calculations of[1]PF_(6) showed that it has a one-electron-reduced ligand,[L]^(·−),which is antiferromagnetically coupled with the low-spin Co(Ⅱ)center that results in an s=0 ground state.[1]PF_(6) showed multiple reversible and quasi-reversible redox events,indicating that it can be explored as a molecular memristor.The indium tin oxide/[1]PF_(6)/Ag memristor demonstrated excellent switching performance with a large ON/OFF ratio(>10^(3)),excellent endurance(>500 cycles),long retention time(>10^(4) s),and long-term stability at an elevated temperature(100℃).Moreover,upon applying pulsed electrical stimuli,the memristor exhibited potentiation and depression behaviors,a key feature for synaptic plasticity.The device was SET at a cathodic potential,and thus,the facile ligand-based reductions in[1]PF_(6) played a decisive role in the device.展开更多
基金the Science&Engineering Research Board(Grant No.CRG/2023/001476)Government of India,for the financial support+6 种基金IIT Jammu for providing seed grant supportUGC and HTRA(MHRD,IIT Jammu)for the fellowship supportthe Council of Scientific and Industrial Research,Govt.of India,for the financial assistanceAnusandhan National Research Foundation(ANRF),Government of India(Grant No.CRG/2022/006352formerly Science&Engineering Research Board),for the financial supportthe Department of Atomic Energy(DAE),Government of India,for the financial support(Grant No.0803/2/2020/NISER/R&D-II/8149)the High-Performance Computing Facility AGASTYA of IIT Jammu.
文摘Achieving multilevel conduction in a cost-effective transition metal complex of a redox-active ligand will be an efficient way for designing a molecular memristor.This study presents a rare example of a tris-azo anion radical ligand-wrapped singlet five-coordinate low-spin Co(Ⅱ)complex,[(L)^(·−)Co(Ⅱ)]PF_(6),[1]PF_(6),that showed solution-processible resistive switching memory with synaptic functionality.The single-crystal X-ray structure,variable-temperature magnetic studies,and DFT calculations of[1]PF_(6) showed that it has a one-electron-reduced ligand,[L]^(·−),which is antiferromagnetically coupled with the low-spin Co(Ⅱ)center that results in an s=0 ground state.[1]PF_(6) showed multiple reversible and quasi-reversible redox events,indicating that it can be explored as a molecular memristor.The indium tin oxide/[1]PF_(6)/Ag memristor demonstrated excellent switching performance with a large ON/OFF ratio(>10^(3)),excellent endurance(>500 cycles),long retention time(>10^(4) s),and long-term stability at an elevated temperature(100℃).Moreover,upon applying pulsed electrical stimuli,the memristor exhibited potentiation and depression behaviors,a key feature for synaptic plasticity.The device was SET at a cathodic potential,and thus,the facile ligand-based reductions in[1]PF_(6) played a decisive role in the device.
