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Copper(II) Dihalotetracyanoplatinate(IV) Coordination Polymers and Their Vapochromic Behavior
Ania S Sergeenko1, Jeffrey S Ovens1, Daniel B Leznoff1
1Department of Chemistry, Simon Fraser University , 8888 University Drive, Burnaby, British Columbia V5A 1S6, Canada.
Inorganic Chemistry
|June 28, 2017
Summary
New coordination polymers form 3-D networks and exhibit vapochromism. The bromine-containing analogue shows a stronger visible color change due to specific electronic transitions, offering potential for sensing applications.
Area of Science:
- Materials Science
- Inorganic Chemistry
- Crystallography
Background:
- Coordination polymers with square grid structures are known for their diverse network topologies.
- Vapochromism, the change in color upon exposure to vapors, is a key property for chemical sensing.
Purpose of the Study:
- To synthesize and characterize new coordination polymers of the form [Cu(H2O)2(μ2-NC)4PtX2] (X = Cl, Br).
- To investigate the structural transformations upon dehydration and their vapochromic, Raman, and IR responses to various analytes.
- To explore the relationship between structural and electronic properties and the observed vapochromic effects.
Main Methods:
- X-ray powder diffraction (PXRD) for structural characterization.
- UV-visible reflectance spectroscopy to study electronic transitions and vapochromism.
- Infrared (IR) and Raman spectroscopy to analyze vibrational responses.
Main Results:
- The synthesized coordination polymers form staggered square grid sheets that transform into 3-D networks upon dehydration.
- Analyte-bound complexes were characterized, revealing similar layered square grid structures.
- The bromine-containing analogue, [Cu(H2O)2(μ2-NC)4PtBr2], exhibited a more pronounced vapochromic effect due to shifted d-d transitions and Br-Pt LMCT absorption.
- Reaction with ammonia yielded distinct platinum-containing anions incorporated into 1-D chains.
Conclusions:
- The coordination polymers [Cu(H2O)2(μ2-NC)4PtX2] can form extended 3-D networks and exhibit tunable vapochromic properties.
- The enhanced vapochromism in the bromine analogue is attributed to specific electronic transitions, highlighting the role of halide identity.
- These materials show potential for developing novel vapor sensors.
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