Optical sensing of aqueous nitrate anion by a platinum(II) triimine salt based solid state material.

Selective and quantitative measurement of aqueous nitrate (NO3-) anion is achieved using solid [Pt(Cl-4-tpy)Cl]ClO4 salt (Cl-4-tpy = 4-chloro-2,2':6'2''-terpyridine), and as the salt supported on controlled porous glass. This detection method relies on the color change of the Pt(II) complex from yellow to red and intense luminescence response upon ClO4- exchange with NO3- due to concomitant enhancement of Pt⋯Pt interactions. The spectroscopic response is highly selective for NO3- over a large range of halides and oxoanions.

Water's Role in Polymorphic Platinum(II) Complexes.

Solvent plays a vital role in the recrystallization process and resulting crystallinity of materials. This role is of such importance that it can control the stability and utility of materials. In this work, the inclusion of a solvent in the crystalline lattice, specifically water, drastically affects the overall stability of two platinum polymorphs. [Pt(tpy)Cl]BF4 (tpy = 2,2';6'2″-terpyridine) crystallizes in three forms, red (1R) and blue (1B) polymorphs and a yellow nonsolvated form (2). 1R is the more stable of the two polymorphs, whereas 1B loses crystallinity upon dehydration at ambient conditions resulting in the formation of 2. Close examination of the solid-state extended structures of the two polymorphs reveals that 1R has a lattice arrangement that is more conducive to stronger intermolecular interactions compared to 1B, thereby promoting greater stability. In addition, these two polymorphs exhibit unique vapochromic responses when exposed to various solvents.

pH-Mediated Colorimetric and Luminescent Sensing of Aqueous Nitrate Anions by a Platinum(II) Luminophore@Mesoporous Silica Composite.

Increased levels of nitrate (NO3-) in the environment can be detrimental to human health. Herein, we report a robust, cost-effective, and scalable, hybrid material-based colorimetric/luminescent sensor technology for rapid, selective, sensitive, and interference-free in situ NO3- detection. These hybrid materials are based on a square-planar platinum(II) salt [Pt(tpy)Cl]PF6 (tpy = 2,2';6',2″-terpyridine) supported on mesoporous silica. The platinum salt undergoes a vivid change in color and luminescence upon exposure to aqueous NO3- anions at pH ≤ 0 caused by substitution of the PF6- anions by aqueous NO3-. This change in photophysics of the platinum salt is induced by a rearrangement of its crystal lattice that leads to an extended Pt···Pt···Pt interaction, along with a concomitant change in its electronic structure. Furthermore, incorporating the material into mesoporous silica enhances the surface area and increases the detection sensitivity. A NO3- detection limit of 0.05 mM (3.1 ppm) is achieved, which is sufficiently lower than the ambient water quality limit of 0.16 mM (10 ppm) set by the United States Environmental Protection Agency. The colorimetric/luminescence of the hybrid material is highly selective to aqueous NO3- anions in the presence of other interfering anions, suggesting that this material is a promising candidate for the rapid NO3- detection and quantification in practical samples without separation, concentration, or other pretreatment steps.

Phase transformation induced mechanochromism in a platinum salt: a tale of two polymorphs.

Red crystals of [Pt(tpy)Cl]NO3·HNO3 show mechanochromic behaviour turning yellow when pressure is applied. The electronic character and spectroscopic signature of the red and yellow polymorphs change as a result of slipping of the molecular stacking planes in the solid state. The slippage alters the PtPt intermolecular distances from a linear stacked motif with <3.5 Å separations in the red polymorph to a less stacked motif of alternating short intradimer and long interdimer interactions in the yellow polymorph.

Luminescent Pt(2,6-bis(N-methylbenzimidazol-2-yl)pyridine)X+: a comparison with the spectroscopic and electrochemical properties of Pt(tpy)X+ (X = Cl, CCPh, Ph, or CH3).

A series of platinum(ii) pincer complexes of the formula Pt(mbzimpy)X+, 1(a-d), (mbzimpy = 2,6-bis(N-methylbenzimidazol-2-yl)pyridine; X = Cl; (a), CCPh; (b), Ph; (c), or CH3; (d), CCPh = phenylacetylide, and Ph = Phenyl) have been synthesized and characterized. Electronic absorption and emission, as well as electrochemical properties of these compounds, have been investigated. Pt(tpy)X+ analogs (tpy = 2,2';6'2''-terpyridine), 2(a-d), have also been investigated and compared. Electrochemistry shows that 1 and 2 analogs undergo two chemically reversible one-electron reduction processes that are shifted cathodically along the a < b < c < d series. Notably, these reductions occur at slightly higher negative potentials in the case of 1. The absorption spectra of 1 and 2 in acetonitrile exhibit ligand-centered (1LC) transitions (ε ≈ 104 M-1 cm-1) in the UV region and metal-to-ligand-charge transfer (1MLCT) transitions (ε ≈ 103 M-1 cm-1) in the visible region. The corresponding visible bands of 1b and 2b have been assigned to 1(LLCT/MLCT) mixed state (LLCT: ligand-to-ligand-charge transfer). The preceding 1LC and 1MLCT transitions of 1 occur at lower energies than that of 2. These 1LC transitions have distinctly been blue-shifted along a < c < d in 2, but occur at nearly identical energies in 1. Conversely, 1MLCT transitions are red-shifted along a < c < d in both the analogs. The 77 K glassy solutions of 1 and 2 exhibit an intense vibronically-structured emission band at λmax(0-0) in the 470-560 nm range. This band is red-shifted along b < a ≤ c < d in 1 and along a ≤ d ≈ c ≪ b in 2. The main character of these emissions is assigned to 3LLCT emissive state in 1b and 2b, whereas to 3LC in the rest of the compounds. Relative stabilization of these spin-forbidden emissive states is discussed by invoking configuration mixing with the higher-lying 3MLCT state.

Solution aggregation of platinum(ii) triimine methyl complexes.

The NMR chemical shifts of [Pt(tpy)(CH3)](PF6) (1) and [Pt(mbzimpy)(CH3)](PF6) (2), where tpy = 2,2';6'2''-terpyridine and mbzimpy = 2,6-bis(N-methylbenzimidazol-2-yl)pyridine, in room-temperature DMSO-d6 displayed concentration dependence as a result of formation of dimers. Quantification of these dimers, expressed by equilibrium constant (K), shows a greater tendency of 2 to aggregate in solution. Structural conformations of these dimers were confirmed by 2D 1H-1H NOESY; the results explicitly suggest a head-to-tail stacking arrangement of molecules in dimers.

A digital imaging method for evaluating the kinetics of vapochromic response.

This work describes the novel use of a cell phone camera and the L*a*b method (color space defined by the International Commission on Illumination) to characterize the color change in different vapochromic platinum(II) complexes in order to get quantitative and more reliable data. In this study, we have developed a semi-automatic CCA software that digitally analyzes images (e.g., video frames) collected while a vapochromic material is absorbing vapor and changing its color. The advantages of using this method, compared to reflectance or transmission spectroscopy through a thin film, include its low cost, convenience, portability, ease of sample preparation, the lack of need for specialized equipment, and the possibility of simultaneously collecting data on different samples under identical conditions. The results show that this strategy is effective in producing quantitative information about the kinetics of processes.

Spectroscopic Characterization of Platinum(IV) Terpyridyl Complexes.

Pt(tpy)X3+ [X = Cl (1), Br (2); tpy = 2,2':6',2″-terpyridine] salts were prepared by the oxidative addition of Pt(tpy)X+ with X2 as originally reported by Morgan and Burstall in 1934. The complexes have been fully characterized by 1H NMR spectroscopy, elemental analysis, mass spectrometry, and X-ray crystallography. The electronic structures of 1 and 2 were investigated using absorption and emission spectroscopy, and the accumulated data are consistent with stabilization of the singlet ligand-centered and potentially singlet ligand field/singlet ligand-to-metal charge-transfer states for 1 and 2 compared to those for Pt(tpy)Cl+ (3) and Pt(tpy)Br+ (4). The changes in the lowest-energy-absorbing state result in drastic differences in the emission behavior among 1-4. Specifically, 1 emits from a lowest-energy state that appears to have triplet ligand field/triplet ligand-to-metal charge-transfer character, whereas 2 exhibits no appreciable emission between 400 and 800 nm.

Synthesis, Luminescence, and Structure of a Polymorphic Polyfluorinated Diiodoplatinum(II) Diimine Complex.

PtI2(5,5'-bis(HCF2CH2OCH2)-2,2'-bpy)], 55-2FH-PtI2, is the first example of a substituted fluorinated diiodoplatinum diimine complex that exhibits polymorphism. The complex, upon recrystallization, forms two different polymorphs, denoted as α and ß forms. The luminescence of the α and ß forms are the same in glassy solution at 77 K; however, in the solid state, they differ significantly. The major difference between them lies in the solid-state packing of the crystalline structure. The α form is a square planar polyfluorinated PtI2-containing complex. Its extended herringbone structure consists of two neighboring stacked bipyridyl planes that do not overlap. The α form emits stronger than its parent molecule, [PtI2bpy], and much stronger than the ß polymorph. The ß form has a slight tetrahedral distortion about the metal center that ultimately changes the geometry of the complex and decreases the d-orbital splitting from square planar. Furthermore, overlapping bipyridine rings in the extended structure of the ß form quench the emission thus resulting in a lower energy emission. Additionally, the ß form shows only one type of C-H···O intermolecular stacking interaction that can cause the moderate distortion of the metal core.

Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes.

An important factor in obtaining reversible multi-electron transfer is overcoming large changes in coordination geometry. One strategy is to use ligands that can support the geometries favored before and after the electron transfer. Pip2NCN- pincer and terpyridine ligands are used to support square planar Pt(ii) and octahedral Pt(iv). For the Pt(ii) complexes, [Pt(Z-pip2NCN)(R-tpy)]+ (Z = NO2, MeO, H; R = H, tertyl butyl, tolyl), 1H NMR spectroscopy shows that the Z-pip2NCN- ligand is monodentate whereas the R-terpyridyl ligand is tridentate. The availability of flanking piperidyl groups of the monodentate pincer ligand is essential for the stabilization of the metal center upon oxidation. Pt(Z-pip2NCN)(R-tpy)+ complexes undergo two-electron platinum centered oxidation near 0.4 V and two Pt(tpy) centered reductions near -1.0 V and -1.5 V. An estimate of n ox/n red = 1.8 is consistent with an oxidation that involves two-electron transfer per Pt center. Variation in the pincer-(Z) and terpyridine-(R) substituents allows for tuning of the oxidation process over a 260 mV range and the two reduction processes over ranges of 230 mV (first reduction) and 290 mV (second reduction step).