abstract
Two monomeric octahedral complexes {[Ni(N(CN)(2))(2)(bpy)(2)](2)center dot H2O (1) and [Mn(N(CN)(2))(2)(bpy)(2)] (2) where bpy = 2,2 '-bipyridine} were synthesized and characterized by single crystal X-ray diffraction, elemental analysis, UV-visible, and IR spectra. The geometry optimization through DFT measurements predicts that both the complexes have similar monomeric structures with hexa-coordinated metal centers having a couple of bpy and mononegative dca anions and thus satisfying the octahedral geometry. Moreover, it is found that the HOMO-LUMO energy gaps are Delta E = 4.981 and 5.563 eV for complexes 1 and 2, respectively, which are responsible for the stabilization of the complex formation. The calculated absorption bands are located at 304 and 235 nm, which are in excellent agreement with the experimental result. Moreover, the DFT study of the electronic spectra of both complexes shows that the calculated absorption bands are in well agreement with the experimental results. In the electrical studies, direct current (dc) measurements on the copper/complex (1 or 2)/copper structure confirm a definite development in the device current with applied bias. Complex 1 has shown better electrical conductance compared to complex 2 based on the reduction of device resistance.
keywords
DENSITY-FUNCTIONAL THEORY; COORDINATION POLYMERS; CRYSTAL-STRUCTURES; HIGHER OLIGOPYRIDINES; EXCITATION-ENERGIES; MAGNETIC-BEHAVIOR; SCHIFF-BASES; LIGAND; MOLECULES; 2,2'-BIPYRIDINE
subject category
Chemistry
authors
Sasmal, P; Debnath, R; Koner, S; Brandao, P; Dolai, M; Bhaumik, PK; Banerjee, A; Ghosh, P; Sinha, D; Chowdhury, A; Das, AK; Mal, D
our authors
Paula Cristina Ferreira da Silva Brandão
Assistant ResearcherProjects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
Dasarath Mal gratefully acknowledges the financial support from the Department of Science & Technology and Biotechnology, Government of West Bengal, by a grant (Grant No. 28(sanc)-ST/P/S&T/15G-4/2018). Paula Brand & atilde;o gratefully acknowledges the financial support of this work by the project CICECO-Aveiro, Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, and LA/P/0006/2020, financed by National funds through the FCT/MCTES. The authors gratefully acknowledge Prof. Kausikisankar Pramanik (Department of Chemistry, Jadavpur University, India) for the help during the manuscript preparation and final revision.