Related Experiment Video
Updated: Jul 10, 2025
16:11
Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
2.3K
Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and
Oksana V Nesterova1, Svitlana R Petrusenko2,3, Brian W Skelton4
1Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Molecules (Basel, Switzerland)
|November 25, 2023
Summary
Three novel heterometallic nickel/cadmium coordination compounds were synthesized. Thermodynamic factors dictate structure, enabling reversible transformations between nickel complexes due to low energy barriers.
Area of Science:
- Coordination Chemistry
- Materials Science
- Computational Chemistry
Background:
- Heterometallic coordination compounds offer tunable properties.
- Self-assembly is a key strategy for constructing complex inorganic structures.
- Understanding structure-property relationships is crucial for materials design.
Purpose of the Study:
- Synthesize novel heterometallic Ni/Cd coordination compounds.
- Investigate the influence of counter-anions and solvents on framework formation.
- Elucidate the electronic structure and ligand substitution mechanisms.
Main Methods:
- One-pot synthesis of Ni/Cd coordination compounds.
- X-ray crystallography for structural determination.
- Density Functional Theory (DFT), CASSCF, and ab initio ligand field theory (AILFT) for electronic structure calculations.
- Quantum Theory of Atoms in Molecules (QTAIM) for analyzing intermolecular interactions.
- High-level computational methods for investigating ligand substitution mechanisms.
Main Results:
- Successfully synthesized three novel heterometallic Ni/Cd coordination compounds: [Ni(en)3][CdCl4]∙3dmso (1), [Ni(en)2(dmf)2][CdBr4] (2), and [Ni(en)3]2[CdI4](I)2 (3).
- Observed the formation of one- or three-dimensional hydrogen-bonded frameworks, dependent on the counter-anion and solvent.
- Electronic structures of key cations were calculated, and non-covalent interactions were analyzed.
- Demonstrated that thermodynamic factors govern structure determination due to low energy barriers for ligand rotation and reversible transformations.
Conclusions:
- The nature of counter-anions and solvents significantly influences the dimensionality of hydrogen-bonded frameworks in these Ni/Cd coordination compounds.
- Thermodynamic control, driven by low energy barriers, plays a critical role in the structural outcomes and interconversion of nickel complexes.
- Computational studies provide deep insights into the electronic properties and reaction mechanisms, aiding in the rational design of novel coordination materials.
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