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Infrared Spectroscopy Studies of Platinum Salts Containing Tetracyanoplatinate(II). Evidence for Strong Hydrogen-Bonding Interactions in “Vapochromic” Environmental Sensor Materials

1998; American Chemical Society; Volume: 10; Issue: 3 Linguagem: Inglês

10.1021/cm970788t

1520-5002

Christopher L. Exstrom, Marie K. Pomije, Kent R. Mann,

Analytical Chemistry and Sensors

We have studied the sorption of volatile organic compounds (VOCs) by [(n-C4H9)4N]2[Pt(CN)4] and [Pt(p-CN-C6H4-C10H21)4][Pt(CN)4] with FTIR spectroscopy. The data indicate a strong correlation exists between ν(CN) stretching frequencies in the [Pt(CN)4]2- ions and the hydrogen bonding ability of the VOC (as expressed by Abraham's α values). The ν(CN) stretching frequencies for each salt with sorbed VOC indicate that similar VOC-material interactions are present in both. The correlation of the IR data for [Pt(p-CN-C6H4-C10H21)4][Pt(CN)4] with the previously reported NIR data was only successful for solvents with α > 0.15. These results suggest that vapochromic shifts in the electronic transitions of [Pt(p-CN-C6H4-C10H21)4][Pt(CN)4] result not only from H-bonds between the VOC and [Pt(CN)4]2- but also from one or more additional mechanisms that are most important for solvents with low H-bond donor character (α < 0.15).