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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
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Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes
Mónica Martínez-Junquera1, Elena Lalinde1, M Teresa Moreno1
1Departamento de Química-Centro de Síntesis Química de La Rioja (CISQ), Universidad de La Rioja, 26006 Logroño, Spain.
Inorganic Chemistry
|July 1, 2022
Summary
New platinum(II) complexes form one-dimensional chains through strong aggregation, leading to sensitive, reversible responses to external stimuli. This supramolecular assembly enables color switching and vapochromic behavior in novel luminescent materials.
Area of Science:
- Coordination Chemistry
- Materials Science
- Photophysics
Background:
- Cyclometalated platinum(II) complexes are known for their interesting photoluminescent properties.
- Supramolecular interactions, such as Pt···Pt and π···π stacking, can significantly influence the solid-state properties of coordination compounds.
- The development of stimuli-responsive materials is crucial for advanced sensing and display technologies.
Purpose of the Study:
- To synthesize and characterize novel neutral, double salt, and cationic cyclometalated platinum(II) complexes with tert-butylisocyanide ligands.
- To investigate the impact of intermolecular aggregation on the photoluminescent properties of these complexes.
- To explore the potential of these complexes as sensitive and reversible sensors for external stimuli.
Main Methods:
- Synthesis and structural characterization of platinum(II) complexes, including pseudopolymorphs.
- Comparative study of solid-state structures and photoluminescent properties.
- Investigation of responses to volatile organic compounds (VOCs), solvents, temperature, and pressure.
- Theoretical simulations of aggregated models to understand photophysical properties.
Main Results:
- Formation of neutral [Pt(C^N)Cl(CNBu^t)] (1), double salt [Pt(C^N)(CNBu^t)_2][Pt(C^N)Cl_2] (2), and cationic [Pt(C^N)(CNBu^t)_2]ClO_4 (3) complexes.
- Strong Pt···Pt and/or π···π stacking interactions lead to one-dimensional infinite chains in pseudopolymorphs.
- Exhibition of highly sensitive and reversible photoluminescent responses (green to red switching) to VOCs, solvents, temperature, and pressure.
- Supramolecular self-assembly into polymer thin films and observation of vapochromic/vapoluminescent behavior.
Conclusions:
- Intermolecular aggregation is the primary driver of the observed photoluminescent behavior and stimuli-responsive properties.
- These platinum(II) complexes demonstrate significant potential as advanced luminescent sensors and responsive materials.
- Theoretical insights support the understanding of photophysical mechanisms in the aggregated solid state.
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