Twisted molecular geometry and localized electronic structure of the triplet excited gem-diphenyltrimethylenemethane biradical: substituent effects on thermoluminescence and related theoretical calculations

Substituent effects on the energies of electronic transitions (ETs) between the triplet excited and ground states of gem-diphenyltrimethylenemethane biradicals (³2a) were explored by using thermoluminescence (TL) spectroscopy and density functional theory (DFT) including time-dependent (TD) DFT. Linear free energy (Hammett) analyses of TL energies of a variety of para-substituted aryl derivatives of ³2* gave reasonable correlations with the substituent constant, σ. The slope of Hammett plots of the data are nearly identical to one obtained from a similar analysis of the photoluminescence (PL) energies of the structurally-related 1,1-diarylethyl radicals (3*). The results suggest that TL of ³2* and PL of 3* derive from a common diarylmethyl radical fluorophore. This interpretation is also supported by the DFT and TDDFT calculated electronic structures and ET energies of ³2 and 3. Thermodynamic and kinetic analyses of the charge recombination (CR) process between 2⁺ and 1⁻, which generates ³2*, revealed that substituents not only alter the TL energies but also the TL intensities of ³2*. The observations made in this effort demonstrate that ³2* as well as ³2 and 2⁺ have greatly twisted molecular geometries and highly localized electronic structures.     

Syntheses, crystal structure and properties of two novel coordination polymers with the flexible tetrazole-1-acetic acid (Htza)

Two new coordination polymers, [Ag(tza)]_∞ (1) (Htza=tetrazole-1-acetic acid) and [Cu(tza)₂]_∞ (2) have been prepared at room temperature and characterized by X-ray crystallography, IR, UV-vis, fluorescence spectra and magnetism analysis. Compound 1 exhibits extended helical chains through bridging ligand tza. The AgAg interactions between the adjacent chains form a 3-D framework featuring the extended tza-connected Ag chains that obviously affect the photoluminescent property. Compound 2 features undulated layered structure with hourglass-shaped [Cu₄(tza)₄] as subunits with the weak ferromagnetic interactions between Cu(II) ions, which are further stabilized by inter-lamellar CHO hydrogen bonds in the resulting 3-D supramolecular framework.     

OH-Induced shift from carbon to oxygen acidity in the side-chain deprotonation of 2-, 3- and 4-methoxybenzyl alcohol radical cations in aqueous solution: results from pulse radiolysis and DFT calculations

DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1⁺, 3⁺ and 4⁺, respectively) and the α-methyl derivatives 2⁺ and 5⁺ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1⁺-5⁺ under acidic and basic conditions. In acidic solution, the decay of 1⁺-5⁺ proceeds by cleavage of the C-H bond, while in the presence of ⁻OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The ⁻OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H₂O, appears to be affected by frontier orbital interactions.     

Determination of photoformation rates and scavenging rate constants of hydroxyl radicals in natural waters using an automatic light irradiation and injection system

Photoformation rates and scavenging rate constants of hydroxyl radicals (OH) in natural water samples were determined by an automatic determination system. After addition of benzene as a chemical probe to a water sample in a reaction cell, light irradiation and injection of irradiated water samples into an HPLC as a function of time were performed automatically. Phenol produced by the reaction between OH and the benzene added to the water sample was determined to quantify the OH formation rate. The rate constants of OH formation from the photolysis of nitrate ions, nitrite ions and hydrogen peroxide were comparable with those obtained in previous studies. The percent of expected OH photoformation rate from added nitrate ion were high in drinking water (97.4%) and river water (99.3%). On the other hand, the low percent (65.0%) was observed in seawater due to the reaction of OH with the high concentrations of chloride and bromide ions. For the automatic system, the coefficient of variance for the determination of the OH formation rate was less than 5.0%, which is smaller than that in the previous report. When the complete time sequence of analytical cycle was 40 min for one sample, the detection limit of the photoformation rate and the sample throughput were 8 × 10⁻¹³ M s⁻¹ and 20 samples per day, respectively. The automatic system successfully determined the photoformation rates and scavenging rate constants of OH in commercial drinking water and the major source and sink of OH were identified as nitrate and bicarbonate ions, respectively.     

Light-emitting persistent radicals for efficient sensor devices of solvent polarity

Radical adduct 1 and the novel [4-(N-indolyl)-2,6-dichlorophenyl] bis(2,4,6-trichlorophenyl)methyl radical (2) exhibit intense fluorescence emission in cyclohexane in the red wavelength region. The intensity and the wavelength of the emission band are drastically dependent on the polarity of the solvent. Besides, radical adduct 2 has been fully characterized by differential scanning calorimeter, showing a high thermal stability and a clear glass nature to form excellent films.     

Factors contributing to one-electron metalloradical activation of ethene and carbon monoxide illustrated by reactions of Co(II), Rh(II), and Ir(II) porphyrins

Metallo-porphyrin complexes of Co(II), Rh(II), and Ir(II) are used as prototype metal-centered radicals in examining the factors that contribute to obtaining one-electron activated ethene and CO substrate adducts [M(CH₂CH₂)] and [M(CO)] that subsequently react on to produce complexes with reduced substrate units including M-CH₂CH₂-M, M-(CH₂)₄-M, M-C(O)-M, M-C(O)-C(O)-M, and M-C(O)H. Cobalt(II) and rhodium(II) complexes of the form [(por)M(CH₂CH₂)] and [(por)M(CO)] occur as primarily metal-centered radicals and the iridium analogs are porphyrin anion radical complexes ((por)⁻Ir^III(CH₂CH₂), (por)⁻Ir^III(CO)). Relatively small (por)Co-C bond dissociation enthalpies preclude forming any reduced substrate species. Rhodium porphyrins produce a complete set of reduced and coupled ethene and CO complexes, but iridium porphyrins only give ethene reduction and coupling products (por)Ir-CH₂CH₂-Ir(por) and (por)Ir-(CH₂)₄-Ir(por). Thermodynamic criteria and analysis of substrate reactions are used to guide interpretations of the observed reactivity.     

The role of oxygen acidity on the side-chain fragmentation of ring methoxylated benzocycloalkenol radical cations

The reactivity of 2,2-dimethyl-5-methoxyindan-1-ol (1) and 2,2-dimethyl-6-methoxytetral-1-ol (2) radical cations has been studied both in acidic and basic solution. At pH≤4 both 1⁺ and 2⁺ undergo C_αH deprotonation as the exclusive reaction with k=4.6×10⁴ and 3.2×10⁴ s⁻¹, respectively. In basic solution 1⁺ and 2⁺ behave as oxygen acids undergoing ⁻OH-induced αOH deprotonation in a diffusion controlled process (k_−OH≈10¹⁰ M⁻¹ s⁻¹). An intermediate alkoxyl radical is formed which undergoes a 1,2-hydrogen atom shift in competition with CC β-scission (with 1⁺) or as the exclusive pathway (with 2⁺). A behavior which is interpreted in terms of the greater ease of ring-opening of a five membered ring as compared to a six-membered one.     

Oxidation of polyethylene under irradiation at low temperature and low dose rate. Part I. The case of “pure” radiochemical initiation

As part of a study on the kinetic modelling of polyethylene oxidation under irradiation at low temperature and low dose rate, this first part deals with the kinetic regime in which thermal initiation, linked to hydroperoxide decomposition, is negligible compared to radiochemical initiation due to polymer radiolysis. The kinetic analysis is based on results published 30 years ago by Decker, Mayo and Richardson. A small modification of their mechanistic scheme, consisting in the introduction of a non-terminating bimolecular combination of PO₂ radicals, leads to a more consistent set of radiochemical yield values. The most significant change is a decrease in the radiochemical yield of radicals G_i from 10 to 8. At 45 °C, termination of PO₂ radicals is not very efficient: 35-40% of the PO₂ + PO₂ encounters are non-terminating, 75% of the termination events lead to peroxide bridges, the rest is a disproportionation according to the Russell mechanism.     

Hole transfer in DNA: DNA as a scaffold for hole transfer between two organic molecules

Hole transfer process in ODNs conjugated with two organic molecules, pyrene (Py) and phenothiazine (Ptz) was investigated with the pulse radiolysis measurements. Monitoring the transient absorption of Py⁺ and Ptz⁺, it was shown that the hole transfer rate was dependent on the distance and sequence between Py and Ptz.     

Spectroscopic and DFT evidence for a nonclassical radical cation derived from 7-benzhydrylidenenorbornene

Nanosecond time-resolved UV/vis absorption spectroscopy on laser flash photolysis was conducted for photoinduced electron-transfer reactions of 7-benzhydrylidenenorbornene (1) and 7-benzhydrylidenenorbornane (5). The differences in the observed absorption bands and the structures of 1⁺ and 5⁺ were evaluated successfully using calculations based on (time dependent) density functional theory, confirming the nonclassical nature of 1⁺.     

Chemiluminescence study of carbonate and peroxynitrous acid and its application to the direct determination of nitrite based on solid surface enhancement

Peroxynitrous acid (ONOOH) was produced by the on-line mixing of acidified hydrogen peroxide with nitrite in a flow system. A strong chemiluminescent (CL) emission was observed when ONOOH reacted with carbonate without any special CL reagents. When cotton was present in the CL cell, the CL emission was enhanced significantly. The method was developed to determine nitrite, which showed a key improvement that any CL reagents and sensitizers were not used, resulting in better selectivity. The applicability of the present CL system was demonstrated for the sensitive and selective determination of nitrite in natural water samples without any special pretreatment. Good agreements were obtained for the determination of nitrite in tap and well waters between the present approach and a standard spectrophotometric method. The average precision was 4.6% (n=7) and detection limit (S/N=3) was 1.0×10⁻⁷ M. Based on the CL spectrum, UV spectra, and dissolved oxygen measurement, a possible CL mechanism was proposed. ONOOH was an unstable compound in acidic solution and could be quenched into peroxynitrite (ONOO⁻) in basic solution. ONOO⁻ reacted with CO₂ to produce ONOOCO₂⁻, which can rapidly decompose into NO₂ and CO₃⁻ radicals. In the presence of H⁺, CO₃⁻ radicals can protonate to bicarbonate radical (HCO₃). The recombination of HCO₃ radicals and decomposition can lead to light emission.