Synthesis of water-soluble Ni(II) complexes and their role in photo-induced electron transfer with MPA-CdTe quantum dots
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Photocatalytic water splitting using solar energy for hydrogen production offers a promising alternative form of storable and clean energy for the future. To design an artificial photosynthesis system that is cost-effective and scalable, earth abundant elements must be used to develop each of the components of the assembly. To develop artificial photosynthetic systems, we need to couple a catalyst for proton reduction to a photosensitizer and understand the mechanism of photo-induced electron transfer from the photosensitizer to the catalyst that serves as the fundamental step for photocatalysis. Therefore, our work is focused on the study of light driven electron transfer kinetics from the quantum dot systems made with inorganic chalcogenides in the presence of Ni-based reduction catalysts. Herein, we report the synthesis and characterization of four Ni(II) complexes of tetradentate ligands with amine and pyridine functionalities (N2/Py2) and their interactions with CdTe quantum dots stabilized by 3-mercaptopropionic acid. The lifetime of the quantum dots was investigated in the presence of the Ni complexes and absorbance, emission and electrochemical measurements were performed to gain a deeper understanding of the photo-induced electron transfer process.
KeywordsNickel complexes Quantum dots Photo-induced electron transfer Biomimetic systems Artificial photosynthesis
Stern–Volmer quenching constant
Bimolecular quenching rate constant
Time-correlated single-photon counting
Valence band energy level
Conduction band energy level
Normal hydrogen electrode
Nuclear magnetic resonance
Electrospray ionization mass spectrometry
This work was funded by the University of Alabama in Huntsville, Individual Investigator Distinguished Research (IIDR) awards to Anusree Mukherjee and Seyed M. Sadeghi.
Compliance with ethical standards
Conflict of interest
The authors declare no competing financial interest.
- Anacona JR, Marquez VE, Jimenez Y (2009) Synthesis and characterization of manganese(II), nickel(II), copper(II) and zinc(II) Schiff-base complexes derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine. J Coord Chem 62(7):1172–1179. https://doi.org/10.1080/00958970802382768 Google Scholar
- Guadalupe Hernandez HJ, Pandiyan T, Bernes S (2006) Mercaptoethanesulfonic acid (CoM imitator) interaction studies with nickel(II) complexes of pyridyl groups containing tetradentate ligands: synthesis, structure, spectra and redox properties. Inorg Chim Acta 359(1):1–12. https://doi.org/10.1016/j.ica.2005.09.036 Google Scholar
- Kankanamalage PHA, Ekanayake DM, Singh N, de Morais ACP, Mazumder S, Verani CN, Mukherjee A, Lanznaster M (2019) Effect of ligand substituents on nickel and copper [N4] complexes: electronic and redox behavior, and reactivity towards protons. New J Chem. https://doi.org/10.1039/C9NJ01283D Google Scholar
- Mautner FA, Mikuriya M, Ishida H, Sakiyama H, Louka FR, Humphrey JW, Massoud SS (2009) Dicyanamido-metal(II) complexes. Part 4: synthesis, structure and magnetic characterization of polynuclear Cu(II) and Ni(II) complexes bridged by μ-1,5-dicyanamide. Inorg Chim Acta 362(11):4073–4080. https://doi.org/10.1016/j.ica.2009.05.066 Google Scholar
- Sadeghi SM, Wing WJ, Gutha RR, Goul RW, Wu JZ (2019) Functional metal-oxide plasmonic metastructures: ultrabright semiconductor quantum dots with polarized spontaneous emission and suppressed auger recombination. Phys Rev Appl 11(2):024045. https://doi.org/10.1103/PhysRevApplied.11.024045 Google Scholar
- Singh N, Niklas J, Poluektov O, Van Heuvelen KM, Mukherjee A (2017) Mononuclear nickel(II) and copper(II) coordination complexes supported by bispicen ligand derivatives: experimental and computational studies. Inorg Chim Acta 455(Part_1):221–230. https://doi.org/10.1016/j.ica.2016.09.001 Google Scholar
- Wang X, Li C (2017) Interfacial charge transfer in semiconductor-molecular photocatalyst systems for proton reduction. J Photochem Photobiol C 33:165–179. https://doi.org/10.1016/j.jphotochemrev.2017.10.003 Google Scholar