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

Abstract

We have studied the sorption of volatile organic compounds (VOCs) by [(n-C 4 H 9 ) 4 N] 2 [Pt-(CN) 4 ] and [Pt(p-CN-C 6 H 4 -C 10 H 21 ) 4 ][Pt(CN) 4 ] with FTIR spectroscopy. The data indicate a strong correlation exists between ν(CN) stretching frequencies in the [Pt(CN) 4 ] 2ions and the hydrogen bonding ability of the VOC (as expressed by Abraham's R 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-C 6 H 4 -C 10 H 21 ) 4 ]-[Pt(CN) 4 ] with the previously reported NIR data was only successful for solvents with R > 0.15. These results suggest that vapochromic shifts in the electronic transitions of [Pt(p-CN-C 6 H 4 -C 10 H 21 ) 4 ][Pt(CN) 4 ] result not only from H-bonds between the VOC and [Pt(CN) 4 ] 2but also from one or more additional mechanisms that are most important for solvents with low H-bond donor character (R < 0.15).

Molecular Accordion: Vapoluminescence and Molecular Flexibility in the Orange and Green Luminescent Crystals of the Dimer, Au2(μ-bis-(diphenylphosphino)ethane)2Br2

“…10À12 Hydrogen bonding between the cyanide ligands and the adsorbed molecules also can play an important role in causing the vapochromic and vapoluminescent changes. 13 The closed-shell, diamagnetic d 10 gold(I) ion produces an interesting array of luminescent complexes with varied properties. 14, 15 Mononuclear, two-coordinate gold(I) complexes are generally colorless and are usually nonluminescent when the individual gold(I) centers are isolated from one another.…”

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η2(π⋅⋅⋅Tl)‐Bonding Interactions

“…[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] In particular, platinum-d 8 complexes have proven to be versatile building blocks for the formation of stacked linearchain materials with short Pt···Pt contacts, [25][26][27][28][29][30] which are notably enhanced by strong-field and p-acidic ligands such as CN À or CNR. Remarkable examples include the wellknown simple, partially oxidized [Pt(CN) 4 ] n 2nÀ salts [31,32] and the double salts [Pt(CNAr) 4 ][Pt(CN) 4 ] reported recently by Mann and co-workers, [33][34][35] which display vapochromic behavior. Considerable experimental work and theoretical calculations [11,36,37] seem to indicate that this type of metalAbstract: A novel series of [PtTl 2 (C CR) 4 ] n (n = 2, R = 4-CH 3 C 6 H 4 (Tol) 1, 1-naphthyl (Np) 2; n = 1, R= 4-CF 3 4 }(acetone)S] 1 (S = acetone 3 a; dioxane 3 b) have been solved by X-ray diffraction studies.…”

Synthesis, Characterization, Spectroscopic, and Electrochemiluminescence Properties of a Solvatochromic Azacrown‐Containing Cyanoruthenate(II): Potential Applications in Separation and Indirect Photometric Detection of Cations and Amino Acids in HPLC

“…[19][20][21] The visible color of the complex was also found to change dramatically from purple to yellow on varying the solvent composition from neat acetonitrile to neat water (Figure 2, bottom). The À were also found to shift in different pH buffer solutions.…”