Study on using I- as heavy atom perturber in cyclodextrin-induced room temperature phosphorimetry

A cyclodextrin induced room temperature phosphorimetry (CD-RTP) for determine beta-NOA, which using I- as a heavy atom perturber (HAP) and sodium sulfite as a deoxygenator, was developed. The phosphorescence peak wavelength maxima lambda(ex)/lambda(em) = 287/496,521 nm. The analytical curve of beta-NOA gives a linear dynamic range of 2.0 x 10(-7)-6.0 x 10(-6) mol/l and a detection limit of 4 x 10(-8) mol/l. The relative standard deviation (RSD; n = 7) was 3.2% for the 4.0 x 10(-6) mol/l beta-NOA in spiked apple samples. The influence of I- concentration on RTP lifetime of beta-NOA was studied in detail, the static Stern-Volmer equation for phosphorescence was derived and the luminescence kinetic parameters were calculated. It is found that the relation between I- concentration (x) and RTP lifetime (tau) can be expressed as tau = 1.047 e(-0.354x) and the rate constants of phosphorescence emission k(p) and non-radiation process k(i) from T1 --> S0 were 0.9551 s(-1) and 0.4276 s(-1) l(-1) mol, respectively.     

Theoretical study of the external heavy atom effect on phosphorescence of free-base porphin molecule

The radiative lifetime of phosphorescence of free-base porphin (H2P) molecule and its complexes with noble-gas atoms are calculated by time-dependent density functions theory (TD DFT) with quadratic response functions for account of spin-orbit coupling and electric dipole activity. The complexes with Ne, Ar, Kr, and Xe are used to simulate the external heavy atom (EHA) effect on phosphorescence of the H2P molecule in the corresponding noble gas matrices. The B3LYP functional and small basis set (3-21G) are used throughout the study and comparison of all complexes but other basis sets are also utilized to support the chosen approach. A slow radiative rate constant of free-base porphin phosphorescence (about 10(-3) s(-1)) is obtained with all basis sets being in the order of magnitude agreement with experimental estimations. A strong enhancement of the H2P phosphorescence rate (by 360 times) is calculated for Xe complex; while for Ne, Ar, and Kr complexes, the enhancement is equal to 1.1, 1.3, and 10.3 times, respectively. In these complexes, the noble gas atom is disposed at 3.6 A above the center of the porphin ring. In spite of shortcomings of the chosen simple model, the TD DFT calculations explain the most important features of the EHA effect on phosphorescence of free-base porphin. Calculations of the hyperfine coupling tensors for all magnetic nuclei in the lowest triplet state of H2P molecule and its complexes with noble-gas atoms indicate an appreciable penetration of the spin density to the EHA region. This can be connected with the enhancement of spin-orbit coupling in the H2P molecule.     

Electronic spectroscopy of toluene-rare-gas clusters: the external heavy atom effect and vibrational predissociation

Toluene-X van der Waals clusters (where X = Ne, Ne2, Ar, Ar2, Kr, Xe) have been investigated by fluorescence excitation spectroscopy in the region of the S1-S0 transition. With the exception of Xe, for each rare-gas studied, we have assigned cluster transitions in the region of all the strong monomer vibrational bands up to 1000 cm(-1) above the origin band. We have further investigated the S1 relaxation dynamics for each vibrational level of each complex, via their fluorescence decay profiles. Clustering with neon has little appreciable effect on the vibrationless S1 lifetime. By contrast, the clusters with argon and krypton exhibit markedly shorter fluorescence lifetimes compared with the monomer. The effect is so severe in the case of toluene-Xe clusters that no fluorescence signals were observed. We interpret these results in terms of an external heavy atom effect in which the rate of intersystem crossing in toluene is influenced by the cluster partner. For clusters built upon excited S1 vibrational levels, the situation is potentially complicated by intramolecular vibrational redistribution and vibrational predissociation (VP). The majority of the fluorescence decay profiles were satisfactorily modeled using single exponential decays. The emission following pumping of the 37(1) level in the toluene-Kr cluster, however, is an exception. We have modeled the decay of this level with a simple kinetic scheme including VP and determined a predissociation rate of (1.04 +/- 0.54) x 10(7) s(-1).     

Selective external heavy atom effect on the dynamics of the isolated triplet sublevels of naphthalene X-traps

We investigated the external heavy atom effect on the dynamics of the isolated sublevels of naphthalene X-traps. The rate constants of the T^x (out of plane) and the T^y (short axis) states are selectively influenced. The heavy atom nearly exclusively affects the radiative decay. Certain symmetry restrictions may affect the external spin-orbit coupling.     

A combined experimental and computational investigation of the microscopic external heavy atom effect in van der Waals clusters

We present a combined experimental and computational study of the external heavy atom effect in van der Waals clusters of para-difluorobenzene (pDFB) with rare-gas atoms. Experimentally, clustering with rare-gas atoms is observed to shorten significantly the S1 fluorescence lifetime compared with that of the pDFB monomer, an effect we interpret in terms of an enhancement of the S1-T1 intersystem crossing rate. In order to test the validity of this widely held assumption, we have calculated the S1-T1 spin-orbit coupling matrix elements in the X-pDFB complexes (X=Ne, Ar, Kr) using a multiconfigurational linear response approach.     

Photochemical dimerization of acephenanthrylene and the heavy atom effect

The solution-phase photodimerization of acephenanthrylene (1) in cyclohexane, chloroform, dibromomethane, and ethyl iodide with visible light (lambda = 419 nm) occurs to form cis (2) and trans (3) photodimers in ratios that vary with the solvent and with the presence or absence of oxygen. The photodimerization exhibits a significant heavy atom effect and also is sensitive to selective quenching by dissolved oxygen, in which only cis stereoisomers are produced. Irradiation of the dimers (lambda = 254 nm) shows that the trans dimers cleave more rapidly than the cis dimers. This is attributed to stabilization of the excited state in the cis dimers.     

Triplet photochemistry within zeolites through heavy atom effect, sensitization and light atom effect

Methods to generate triplets of organic molecules within zeolites have been established by employing the Zimmerman rearrangement of barrelenes, oxa-di-π-methane rearrangement of β,γ-unsaturated ketones and photodimerization of acenaphthylene as probe reactions. The two methods, heavy cation effect and triplet sensitization, are well established solution techniques and these work well within zeolites. The Zimmerman rearrangement of dibenzobarrelene is enhanced even within Li⁺ and Na⁺ exchanged zeolites and these are believed to be the result of slowing of the rearrangement to dibenzocyclooctatetraene from S₁ through cation-π interaction. The methods described here provide an opportunity to explore the control afforded by the zeolite environment on triplet reactions.     

External heavy atom effect on radiative spin-forbidden transitions

A general model for the external heavy atom effect on radiative transitions within the framework of the dynamic coupling model is proposed. The two different mechanisms are considered, the spin-orbit coupling mechanism and the polarizability mechanism. The question of whether the polarizability of the heavy atom perturber determines the magnitudes of the effect is discussed.     

On the heavy atom on light atom relativistic effect in the NMR shielding constants of phosphine tellurides

The relativistic HALA effect has been shown to depend on the spatial deformation of the lone electron pairs of a heavy atom, as demonstrated for alkyl and alkene phosphine tellurides. It was found that HALA effect on phosphorous nuclear magnetic resonance shielding constant is strongly dependent on the spatial arrangements of light substituents on phosphorus, resulting in the deformation of the lone electron pairs of tellurium.     

Effect of an external heavy atom on the EPR spectrum of the fluorescein semiquinone radical

The effect of an external heavy atom on the EPR spectra of radicals in homogeneous liquid solutions was investigated. Broadening of the lines in the EPR spectrum of the fluorescein semiquinone radical in water-ethanol solution was found under the effect of the external heavy atom. It was hypothesized that this broadening is due to an increase in the anisotropy of the g-factor due to potentiation of the spinorbital interaction on contact with the external heavy atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1778–1781, August, 1989.We would like to thank V. A. Roginskii for his assistance in the research and valuable advice, and B. F. Minaev for his useful discussion of the mechanism.     

Position-dependent heavy atom effect in the subrates of the lowest triplet state of dichloronaphthalenes

By means of the microwave-induced delayed phosphorescence (MIDP) technique, the dynamics of the lowest triplet state T₀ of several dichloronaphthalenes in naphthalene and durene are investigated. It is shown that the position dependence is very selective in the nonradiative decay of the spin-sublevels: The out-of-plane spin state is nearly not affected, while the in-plane states are strongly affected. The radiative rates, on the other hand, are not selectively influenced by the position of substitution. Besides, the results show that the dynamics of the lowest triplet state is determined by the type of substitution, rather than by the symmetry of the molecule. The spin—orbit coupling of the in-plane states seems to profit from some distortion the guest molecule experiences in the naphthalene host lattice.     

Position dependent heavy atom effect in physical triplet quenching by electron donors

The radical yields and rate constants in the quenching reaction of thionine triplet with the complete series of monohalogen substituted anilines as electron donors were determined by flash spectroscopy. Whereas the quenching rate constants show little and unsystematic variation, the radical yields decrease with increasing spin—orbit coupling constant of the halogen substituent. This effect is very sensitive to the position of the halogen in the donor. The results are explained in terms of a heavy atom effect on the intersystem crossing rate constant in a triplet exciplex.     

Spin-canting in heavy atom heterocyclic radicals

A pair of isostructural bis-selenathiazolyl and bis-diselenazolyl radical conductors display weak (spin-canted) ferromagnetism with Tc values of 18 K and 27 K respectively.     

The heavy atom effect on photocleavage of DNA by mono-hydroxyl halogenated corroles

<正>DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA(SC) into nicked-circular DNA(NC).The activity of these corroles follows an order of 432≈15.The photosensitized singlet oxygen(Φ_△) quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.     

The study of the intramolecular heavy atom effect in 9,10-dichlorophenanthrene and 1,2,3,4-tetrachloronaphthalene using PMDR techniques

Using PMDR techniques, the top two zero-field triplet levels in 9,10-dichlorophenanthrene and 1,2,3,4-tetrachloronaphthalene are shown to be most favoured by S₁ → T₁ ISC and T₁ → S₀ phosphorescence. Spin—orbit vibronic coupling via CCl out-of-plane modes and static distortions of the heavy atom are responsible for such behaviour respectively.     

Magnetic anisotropy in a heavy atom radical ferromagnet

High-field, single-crystal EPR spectroscopy on a tetragonal bisdiselenazolyl ferromagnet has provided evidence for the presence of easy-axis magnetic anisotropy, with the crystallographic c axis as the easy axis and the ab plane as the hard plane. The observation of a zero-field gap in the resonance frequency is interpreted in terms of an anisotropy field several orders of magnitude larger than that observed in light-heteroatom, nonmetallic ferromagnets and comparable (on a per-site basis) to that observed in hexagonal close packed cobalt. The results indicate that large spin-orbit-induced magnetic anisotropies, typically associated with 3d-orbital-based ferromagnets, can also be found in heavy p-block radicals, suggesting that there may be major opportunities for the development of heavy p-block organic magnetic materials.