PVK三线态激基复合物的发光及其受紫外光辐照的影响

用不同溶剂中的前驱物旋涂成PVK层,制备了ITO/PEDOT:PSS/PVK/Ca:Al器件,以及相同结构不同PVK分子量的器件。通过测试分析认为:器件的电致发光谱中590nm波长处的发光峰来自于PVK三线态的激基复合物,并且发现其强度依赖于PVK的分子构型,即在PVK分子中相邻咔唑基团重叠程度。通过比较不同紫外辐照剂量后的PVK器件的发光,发现适度的UV辐照后的PVK分子构型中相邻咔唑基团处于全重叠的状态增加,在电致发光时会形成更多的三线态激子,因而提高了PLED器件的发光效率。     

掺杂型有机电致发光二极管的研究进展

有机电致发光具有结构简单、成本低、平面光源、节省能源等优点,其中掺杂型电致发光二极管因可以同时利用单重态和三重态的激子来发光和理论上能使器件内量子效率达到100%而倍受关注。从掺杂型电致发光二极管发光机理、主体材料、掺杂剂材料、白光器件几个方面阐述了该领域的研究进展。     

Boundary relations and their Weyl families

The concepts of boundary relations and the corresponding Weyl families are introduced. Let be a closed symmetric linear operator or, more generally, a closed symmetric relation in a Hilbert space , let be an auxiliary Hilbert space, let

and let be defined analogously. A unitary relation from the Krein space to the Krein space is called a boundary relation for the adjoint if . The corresponding Weyl family is defined as the family of images of the defect subspaces , , under . Here need not be surjective and is even allowed to be multi-valued. While this leads to fruitful connections between certain classes of holomorphic families of linear relations on the complex Hilbert space and the class of unitary relations , it also generalizes the notion of so-called boundary value space and essentially extends the applicability of abstract boundary mappings in the connection of boundary value problems. Moreover, these new notions yield, for instance, the following realization theorem: every -valued maximal dissipative (for ) holomorphic family of linear relations is the Weyl family of a boundary relation, which is unique up to unitary equivalence if certain minimality conditions are satisfied. Further connections between analytic and spectral theoretical properties of Weyl families and geometric properties of boundary relations are investigated, and some applications are given.

     

Lepton-number-violating decays of singly-charged Higgs bosons in the type-（Ⅰ＋Ⅱ ） seesaw model

The lepton-number-violating decays of singly-charged Higgs bosons H^± are investigated in the minimal type-（ Ⅰ＋Ⅱ ） seesaw model with one SU（2）L Higgs triplet △ and one heavy Majorana neutrino N1 at the TeV scale. We find that the branching ratios B（H^＋ → 1α^＋υ^-） （for α = e,μ,τ） depend not only on the mass and mixing parameters of three light neutrinos υi （for i = 1, 2, 3） but also on those of N1. Assuming that the mass of N1 lies in the range of 200 GeV to 1 TeV, we figure out the generous interference bands for the contributions of υi and N1 to B（H^＋→ 1α^＋υ^-）. We illustrate some salient features of such interference effects by considering three typical mass patterns of υi, and show that the relevant Majorana CP-violating phases can affect the magnitudes of B（H^＋→ 1α^＋υ^-）） in this parameter region.     

Electron spin polarisation in the photoreduction of xanthone in alcohol: effect of concentration and temperature

Time-resolved EPR studies of the hydrogen abstraction reaction of photoexcited xanthone in 2-propanol were carried out as a function of the concentration of xanthone and the sample temperature. The temperature was varied from 22°C to about ?30°C, and the concentration from about 0.2 to 4.0?mM. At low temperature or concentration, the observed spectra of the xanthone ketyl radical and the propan-2-olyl radical could be simulated as a superposition of a hyperfine-independent component due to the emissive triplet mechanism and a hyperfine-dependent component due to the S–T₀ radical pair mechanism. However, with an increase in the concentration of xanthone, the relative contribution of TM decreases, and, concomitantly, the net absorptive component of only the xanthone ketyl radical increases. As the spin polarisation mechanisms do not predict any concentration dependence, this unusual behaviour is explained by invoking the enhancement of the spin–lattice relaxation rates due to Heisenberg spin exchange occurring at high local concentrations of the radicals. The net absorptive signal is attributed to thermally equilibrated radicals. The observed temperature dependence of the spin polarisation behaviour is similarly explained. The origin of the net absorptive signal in the TREPR spectra of the acetone?2-propanol system is also attributed to thermally equilibrated radicals. The self-quenching mechanism of xanthone is proposed to be an electron-transfer reaction from an excited xanthone molecule to another xanthone in the ground state.     

Synthesis,Photophysics and Redox Properties of Aza-BODIPY Dyes with Electron-Donating Groups

A series of novel aza-BODIPY dyes substituted with p-(dimethylamino)phenyl groups were synthesized and their spectral and electrochemical properties were compared. In particular, the impact of p-(Me₂N)Ph- groups on these characteristics was of consideration. For two aza-BODIPYs studied, a near-IR absorption band was observed at circa λ_abs=796 nm. Due to the pronounced intramolecular charge transfer (ICT) exerted by the presence of strongly electron-donating p-(Me₂N)Ph- substituents, the compounds studied were weakly emissive with the singlet lifetimes (τ_S) in the picosecond range. Nanosecond laser photolysis experiments of the brominated aza-BODIPYs revealed T₁→T_n absorption spanning from ca. 350 nm to ca. 550 nm with the triplet lifetimes (τ_T) ranged between 6.0 μs and 8.5 μs. The optical properties of the aza-BODIPYs studied were pH-sensitive. Upon protonation of the dimethylamino groups with trifluoroacetic acid in toluene, a stepwise disappearance of the NIR absorption band at λ_abs=790 nm was observed with the concomitant appearance of a blue-shifted absorption band at λ_abs=652 nm, which was accompanied by a prominent emission band at λ_fl=680 nm. The transformation from a non-emissive to an emissive compound is associated with the inhibition of the ICT. As estimated by CV/DPV measurements, all aza-BODIPYs studied exhibited two irreversible oxidation and two quasi-reversible reduction processes. All compounds studied exhibit extremely high photostability and thermal stability.     

Magnetic field as a means to identify initiating reaction in oxidation of organic substances with molecular oxygen

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Iridium(III) Complexes Bearing Pyrene‐Functionalized 1,10‐Phenanthroline Ligands as Highly Efficient Sensitizers for Triplet–Triplet Annihilation Upconversion

“Chemistry‐on‐the‐complex” synthetic methods have allowed the selective addition of 1‐ethynylpyrene appendages to the 3‐, 5‐, 3,8‐ and 5,6‐positions of Ir^III‐coordinated 1,10‐phenanthroline via Sonogashira cross‐coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8‐substituted Ir‐3 : λ_abs=481 nm, ?=52 400 m ^?1 cm^?1) and long‐lived triplet excited states (e.g. 5‐substituted Ir‐2 : τ_T=367.7 μs) were observed for the complexes in deaerated CH₂Cl₂. On testing the series as triplet sensitizers for triplet–triplet annihilation upconversion, those Ir^III complexes bearing pyrenyl appendages at the 3‐ and 3,8‐positions ( Ir‐1 , Ir‐3 ) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively).     

On the conjugation length for oligo(ethynylnaphthalene)-based molecular rods

The synthesis is described for a small series of oligomers built from (2, 3, 4 or 6) ethynyl-naphthalene repeat units and end-capped with solubilising 1,2,3-tris-dodecyloxy-benzene groups. These compounds absorb in the near-UV region and exhibit strong fluorescence in both fluid solution and a glassy matrix at 77 K. The spectral profiles are fully consistent with a structurally heterogeneous ground state becoming more planar upon excitation and with the low-temperature glass further stabilising the co-planar orientation. The absorption and fluorescence maxima move towards lower energy with increasing number of repeat units and there is a corresponding increase in the Huang-Rhys factor for the radiative process. The non-radiative rate constants also depend on molecular length and are well explained in terms of the energy-gap law. In contrast, very weak phosphorescence is observed at 77 K for which the peak maximum and lifetime remain insensitive to the number of naphthalene units. The triplet lifetimes recorded at ambient temperature are also independent of the molecular length but the triplet-triplet absorption spectra change throughout the series. These results are discussed in terms of the degree of electronic coupling between adjacent repeat units for each of the relevant excited states. During these studies it was noted that the rate of intersystem crossing to the triplet manifold is but weakly affected by heavy-atom perturbers. A non-fluorescent complex is formed between iodoethane and the molecular rod but the corresponding bimolecular process occurs at well below the diffusion-controlled limit. This behaviour is considered in terms of spin-orbit coupling between the excited states and takes account of the differing conjugation lengths.     

C-O-bond cleavage of esters with a naphthyl group in the higher triplet excited state during two-color two-laser flash photolysis

A C-O-bond cleavage of esters having a naphthyl group, NpCO-OR and RCO-ONp (Np=alpha- and beta-naphthyl ((alpha)Np and (beta)Np, respectively), R=Ph and Me), was found during the two-color two-laser flash photolysis in acetonitrile. The C-O-bond cleavage occurred when NpCO-OR and RCO-ONp were excited to the singlet excited states (S1). On the other hand, no reaction occurred from the lowest triplet excited states (T1). When NpCO-OR(T1) and RCO-ONp(T1) were excited to the higher triplet excited states (Tn) using the second laser during the two-color two-laser flash photolysis, the C-O-bond cleavage occurred. The C-O-bond cleavage quantum yield (Phi) was estimated from the plots of the T1-state esters disappeared within a laser flash versus the second laser intensities. The C-O-bond cleavage in (beta)NpCO-OPh(Tn) occurred more efficiently than in (alpha)NpCO-OPh(Tn) and that in PhCO-O(beta)Np(Tn) occurred more efficiently than in PhCO-O(alpha)Np(Tn). The Phi value for ester with Ph and beta-Np groups was larger than that for ester with Ph and alpha-Np groups. The Phi value for MeCO-O(alpha)Np(Tn) was similar to those for PhCO-ONp(Tn), while that for MeCO-O(beta)Np(Tn) was much smaller than those for PhCO-ONp(Tn) and MeCO-O(alpha)Np(Tn). On the other hand, no C-O-bond cleavage was observed in NpCO-OMe(Tn). The Phi value depended on the characters of the groups (Np, Ph, and Me) on the ester. Whether R is Ph or Me with or without pi electron, respectively, is important for the C-O-bond cleavage. In other words, electronic delocalization of the T(n) state including Np and ester groups is necessary for the occurrence of the C-O-bond cleavage in NpCO-OR(Tn) and RCO-ONp(Tn).