Abstract
The formation of the symmetrical μ3-carbonate-bridged self-assembled trinuclear NiII complex Na2{[Ni(LO)2(H2O)]3(μ3-CO3)} (LO is the carboxylate anion of a L-tyrosine derivative), involves atmospheric CO2 uptake. The asymmetric unit of the complex comprises an octahedral coordination for the NiII with two L-tyrosine-based ligands, a water molecule and one O atom of the carbonate bridge. The Ni3-μ3-CO3 core in this compound is the first reported of this kind according to the Cambridge Structural Database (CSD). The supramolecular structure is mainly sustained by hydrogen bonds developed by the phenolic functionality of the L-tyrosine moiety of one ligand and the carboxylate group of a neighbouring ligand. The crystal packing is then characterized by three interpenetrated supramolecular helices associated with a diastereoisomer of the type R-supP, which is essential for the assembly process. Magnetic susceptibility and magnetization data support weak ferromagnetic exchange interactions within the novel Ni3-μ3-CO3 core. The NiII complex obtained under the same synthetic conditions but using the analogous ligand derived from the amino acid L-phenylalanine instead of L-tyrosine gives rise to to a mononuclear octahedral system. The results obtained for the different complexes demonstrate the role of the supramolecular structure regarding the CO2 uptake property for these NiII-amino-acid-based systems.
Highlights
The fixation of CO2 by nickel ions in basic solutions and the subsequent generation of a carbonate complex is relevant to the bioinorganic, environmental, structural and materials chemistry fields
We observed that CO2 air fixation is a critical tool in the assembly of an l-Tyr-based trinuclear NiII complex
It is suggested that the self-assembly process and the resulting structure is governed by the nature of the amino acid derivative through the supramolecular structure that is developed
Summary
The fixation of CO2 by nickel ions in basic solutions and the subsequent generation of a carbonate complex is relevant to the bioinorganic, environmental, structural and materials chemistry fields. The carbonate ion is a very versatile ligand, since each O atom may act in a mono- or bidentate manner, and it is able to produce bi-, tri-, tetra-, penta- and hexanuclear coordination systems This characteristic makes the carbonate ligand an interesting source for the design and synthesis of structurally rich complexes. An updated descriptive statistical analysis using the hits obtained from the CSD showed that every coordination mode is not found, modes 1 and 3 being the most common having 24 and 19% of the total, respectively (Fig. 1 and supporting information) They are followed by mode 8 (bridging 3carbonate) with 17% and mode 2 with 15% of the total. The most frequently observed mode is mode 8 (supporting information)
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Acta crystallographica Section B, Structural science, crystal engineering and materials
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
