Medium-sized cyclophanes—XVII : Tetra-, hexa-, octa- and decahydropyrenes from [2.2]metacyclophane. Transannular dehydrogenation,isomerization, and disproportionation reactions by means of benzoyl peroxide,metal salts and sulfuric acids

[2.2]Metacyclophane (1) undergoes a variety of reactions according to the reagents and conditions. These include (1) substitution (path a), (2) transannular dehydrogenation (path b and c), (3) cycloisomerization (path d) and (4) transannular hydrogenation. A brief summary of these reactions is presented.The diversity of the reactions of 1 is further explored using benzoyl peroxide (BPO), cupric chloride, aluminum chloride, other metal salts, H₂SO₄ and FSO₃H. With BPO or cupric chloride, one-electron transfer mechanism is postulated. This involves a tautomeric ion pair formed by the intramolecular arylation with an aryl cation radical. A supporting evidence in favor of the mechanism is presented from experiments using various metal salts in different solvents.On the contrary, the reaction with aluminum chloride gives decahydropyrene (8) and octahydropyrene (11) together with cycloisomerization product 5 and dehydrogenation products 2, 3 and 4. When treated with AlCl₃HCl 1 gives similar products as above but the product ratios are quite different. The major product is 5 but only a trace amount of 8 is formed. The reaction with H₂SO₄ or FSO₃H also produce 2, 4, 5 and 11. Some mechanistic evidence in favor of the disproportionation reaction is presented.     

Relaxed excited states and anomalous hyperfine structure of muonium centers in KBr

We report on the luminescence induced by positive muons implanted (with 4 MeV) into KBr crystal, which evidences a long-lived (lifetime=13.3 s excited state produced by muon radiolysis. The temperature dependence of the luminescence yield has a strong correlation with the amplitude of an anomalous muonium center: both are observed only below 50 K. This correlation strongly suggests that the muonium center is perturbed by the muon-induced excitons to cause the anomalous hyperfine structure. Moreover, the luminescence energy and decay time indicate that the observed luminescence is not associated with the intrinsic or impurity-related self-trapped excitons, but with a relaxed excited state specific to the muon(ium)-KBr system.     

Novel one-dimensional tubelike and two-dimensional polycatenated metal-organic frameworks

Two novel metal-organic frameworks (MOFs) [Zn(TITMB)(OAc)](OH).8.5H(2)O (1) and [Ag(TITMB)N(3)].H(2)O (2) [TITMB = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, OAc = acetate anion] were synthesized and their structures were determined by X-ray crystallography. Complex 1 crystallizes in tetragonal space group P(-)4 with a = 23.2664(7) and c = 11.9890(3) A and Z = 8. 1 has a one-dimensional tubelike structure with large inner pore size of approximately 17 A. Complex 2 crystallizes in monoclinic space group C2 with a = 20.7193(10), b = 11.5677(8), and c = 12.2944(6) A, beta = 125.5770(10) degrees, and Z = 4. 2 consists of two-dimensional honeycomb networks that interpenetrate each other to generate a polycatenated structure. In these two complexes, both zinc(II) and silver(I) atoms are four-coordinated with the same tetrahedral coordination geometry. The topologies of 1 and 2 are predominated by the conformations of TITMB, which are cis, trans, trans in 1 and cis, cis, cis in 2, respectively.     

Effect of ginseng saponins on the survival of cerebral cortex neurons in cell cultures

The effects of nerve growth factor (NGF) and saponins isolated from Panax ginseng C.A. Mayer on the survival of chick and rat embryonic cerebral cortex neurons were examined. Ginsenoside Rg1 (GRg1) exerted a survival-promoting effect on both chick and rat cerebral cortex neurons in cell cultures. Ginsenoside Rb1 (GRb1) also had an effect in the rat and displayed some influence in the chick. NGF alone exerted no effect on both neurons, although it did potentiate the GRb1 effect on chick embryonic cerebral cortex neurons, but did not alter the GRb1 effect on rat embryonic cerebral cortex neurons. NGF did not alter the survival-promoting effect of GRg1 on either chick or rat embryonic cerebral cortex neurons. The other saponins alone or with NGF exerted no effect on the survival of cerebral cortex neurons in either the chick or rat.     

Light emission from chlorine atoms formed in the dissociative excitation of HCI in a flowing afterglow of discharged argon

Light emission from Cl(5p) atoms (near 440 nm) produced in the reaction of HCl in a discharged flow of argon was investigated with a flowing-afterglow apparatus. Ionic species, most probably argon ions in metastable states, Ar^+M, were found to be responsible for the Cl(5p) production in the dissociative excitation of HCl.     

Muon spin relaxation for Ar+NO2 systems in transverse and longitudinal magnetic fields

Surface muons produced in UT-MSL were introduced into argon gas of 4.0±0.2 atm with NO₂ (0–30 ppm), and muonium signals were detected in the presence of a transverse (1.7–3.4 G) and a longitudinal magnetic field (0–3.5 kG) at 295±1 K. The cross section for the transverse relaxation was (11.0±1.0)×10⁻¹⁶ cm². The relaxation rates in different longitudinal magnetic fields show that the rate does not follow the conventional equation which assumes that the relaxation occurs mainly by spin-exchange interaction. Similar measurements were performed for the Mu+O₂ system. These findings indicate that chemical reactions contribute to these relaxation rates.     

Spin dynamics in crystalline and amorphous DyAg

Crystalline (cr-) Dyag [CsC] structure] orders antiferro-magnetically with T_N≅60K; amorphous (am-) DyAg ferro-magnetically with T_C≈-18K. We measured the longitudinal field (LF) μ⁺SR relaxation functions G_ZZ(t) for 5K<T<300K using surface muons. In the paramagnetic state. cr-DyAg gives an exponential G_ZZ (t) in the relaxation rate rising first slowly then more rapidlynear T_N; no decoupling is observed in LF up to 0.4T. In the ordered state we see a Lorentzian Kubo-Toyabe G_ZZ(t), becoming nearly static at the lowest temperatures. Its static width is very narrow (Δ≈-7 MHz), and full dceoupling is achieved here in 0.1 T. On approaching T_N, the fluctuation rate and the static width increase mootonically bt the field distribution remains Loratzian. A LF of 0.4T is then insufficient to quench the fast exponential relaxation. In paramagnetic am-DyAg, the μ⁺ depolarization is always much faster then in cr-DyAg. At lower temperatures it is better described by a root-exponential than an exponential G_ZZ(t). Below T_C an exponentially relaxing signal with 1/3 amplitude is seen. The decoupling effect of LF up to 0.4T was negligible at all temperatures.