Thermochromic Absorption And Photoluminescence In [pt(ppy)(mu-ph(2)pz)](2)

The temperature effects on the spectral properties and photophysics of a new d(8)-d(8) dinuclear Pt-II chromophore, [Pt(ppy)(mu-Ph(2)pz)](2) (ppy is 2-phenylpyridine and Ph(2)pz is 3,5-diphenylpyrazolate), have been investigated. The thermochromic shifts are tentatively ascribed to intramolecular sigma interactions between the two pseudocofacial d(Z2) orbitals. Substantial emission profile changes occur in the solid state, solution, and doped polymer films

Luminescent Charge-transfer Platinum(ii) Metallacycle

The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2\u27-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4\u27-di-tert-butyl-2,2\u27-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively, The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH2Cl2, 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH2Cl2 and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3 does not possess any charge-transfer character, excitation into the pi pi* transitions of the tda ligand generated transient absorptions in the relaxed excited state assigned to the ligand-localized triplet state. In all three cases, the excited-state lifetimes measured by transient absorption are similar to those measured by time-resolved photoluminescence, suggesting that the same excited states giving rise to the photoluminescence are responsible for the absorption transients. ESR spectroscopy of the anions 1(-) and 2(-) and reductive spectroelectrochemistry of 1 and 2 revealed a LUMO based largely on the pi* orbital of the dbbpy ligand. Time-dependent density functional theory calculations performed on 1-3 both in vacuum and in a CH2Cl2 continuum revealed the molecular orbitals, energies, dipole moments, and oscillator strengths for the various electronic transitions in these molecules. A Delta SCF-method-derived shift applied to the calculated transition energies in the solvent continuum yielded good agreement between theory and experiment for each molecule in this study

Electronic and Steric Effects on the Photoisomerization of Dimethylsulfoxide Complexes of Ru(II) Containing Picolinate

Calculations were performed on [Ru(tpy)(bpy)(dmso)]²⁺ (tpy = 2,2′:6′,2′′-terpyridine; bpy = 2,2′-bipyridine, dmso = dimethylsulfoxide, <b>1</b>), <i>cis</i>-[Ru(tpy)(Me-pic)(dmso)]⁺ (Me-pic = 6-methylpicolinate, <b>2</b>), <i>trans</i>-[Ru(tpy)(Me-pic)(dmso)]⁺ (<b>3</b>), and <i>trans</i>-[Ru(tpy)(pic)(dmso)]⁺ (pic = picolinate, <b>4</b>) to gain an understanding of the differences in their photoisomerization behavior. The results do not support a promoting role for the σ* ligand field (LF) states during excited-state S→O isomerization. Instead, the calculations show that the Ru−S bonding, the identity of the highest occupied molecular orbital, and steric interactions are important factors in dmso photoisomerization. Furthermore, the atom positioned trans to the S atom plays a critical role in promoting enhanced photoisomerizataion yields

Controlled Release of Antimicrobial ClO₂ Gas from a Two-Layer Polymeric Film System

We report a two-component label system comprising a chlorite-containing polymer film and an acid-containing polymer film that can release antimicrobial ClO₂ gas upon adhering the two films together to enable a reaction of the chlorite and acid under moisture exposure. The chlorite-containing film comprises a commercial acrylate-based pressure-sensitive adhesive polymer impregnated with sodium chlorite. The acid-containing film comprises a commercial poly­(vinyl alcohol) polymer loaded with tartaric acid. Both of the films were prepared on low ClO₂-absorbing substrate films from stable aqueous systems of the polymers with high reagent loading. Rapid and sustained releases of significant amounts of ClO₂ gas from the label system were observed in an in situ quantification system using UV–vis spectroscopy. It was found that the ClO₂ release is slower at a lower temperature and can be accelerated by moisture in the atmosphere and the films. Controlled release of ClO₂ gas from the label system was demonstrated by tailoring film composition and thickness. A model was developed to extract release kinetics and revealed good conversions of the label system. This two-component system can potentially be applied as a two-part label without premature release for applications in food packaging

Driving Force Dependence of Electron Transfer from Electronically Excited [Ir(COD)(μ-Me_2pz)]_2 to Photo-Acid Generators

We report the rates of electron transfer (ET) reactions of electronically excited [Ir(COD)(μ-Me_2pz)]_2 with onium salt photoacid generators (PAGs). The reduction potentials of the PAGs span a large electrochemical window that allows determination of the driving force dependence of the ET reactions. Rate constants of ET from electronically excited [Ir(COD)(μ-Me_2pz)]_2 to onium PAGs are determined by the reaction driving force until the diffusion limit in acetonitrile is reached

Triplet Excited State Distortions in a Pyrazolate Bridged Platinum Dimer Measured by X-ray Transient Absorption Spectroscopy.

The excited-state structure of a dinuclear platinum(II) complex with tert-butyl substituted pyrazolate bridging units, [Pt(ppy)(μ-(t)Bu(2)pz)](2) (ppy = 2-phenylpyridine; (t)Bu(2)pz = 3,5-di-tert-butylpyrazolate) is studied by X-ray transient absorption (XTA) spectroscopy to reveal the transient electronic and nuclear geometry. DFT calculations predict that the lowest energy triplet excited state, assigned to a metal-metal-to-ligand charge transfer (MMLCT) transition, has a contraction in the Pt-Pt distance. The Pt-Pt bond length and other structural parameters extracted from fitting the experimental XTA difference spectra from full multiple scattering (FMS) and multidimensional interpolation calculations indicates a metal-metal distance decrease by approximately 0.2 Å in the triplet excited state. The advantages and challenges of this approach in resolving dynamic transient structures of nonbonding or weak-bonding dinuclear metal complexes in solution are discussed