Facially coordinating triamine ligands with a cyclic backbone: some structure-stability correlations

Metal complex formation of the two cyclic triamines 6-methyl-1,4-diazepan-6-amine (MeL(a)) and all-cis-2,4,6-trimethylcyclohexane-1,3,5-triamine (Me(3)tach) was studied. The structure of the free ligands (H(x)MeL(a))(x+) and H(x)Me(3)tach(x+) (0 ≤ x ≤ 3) was investigated by pH-dependent NMR spectroscopy and X-ray diffraction experiments. The crystal structure of (H(2)Me(3)tach)(p-O(3)S-C(6)H(4)-CH(3))(2) showed a chair conformation with axial nitrogen atoms for the doubly protonated species. In contrast to a previous report, Me(3)tach was found to be a stronger base than the parent cis-cyclohexane-1,3,5-triamine (tach); pK(a)-values of H(3)Me(3)tach(3+) (25 °C, 0.1 M KCl): 5.2, 7.4, 11.2. The crystal structures of (H(3)MeL(a))(BiCl(6))·2H(2)O and (H(3)MeL(a))(ClO(4))Cl(2) exhibited two distinct twisted chair conformations of the seven membered diazepane ring. [Co(MeL(a))(2)](3+) (cis: 1(3+), trans: 2(3+)), trans-[Fe(MeL(a))(2)](3+) (3(3+)), [(MeL(a))ClCd(μ(2)-Cl)](2) (4), trans-[Cu(MeL(a))(2)](2+) (5(2+)), and [Cu(HMeL(a))Br(3)] (6) were characterized by single crystal X-ray analysis of 1(ClO(4))(3)·H(2)O, 2Br(3)·H(2)O, 3(ClO(4))(3)·0.8MeCN·0.2MeOH, 4, 5Br(2)·0.5MeOH, and 6·H(2)O. Formation constants and redox potentials of MeL(a) complexes were determined by potentiometric, spectrophotometric, and cyclovoltammetric measurements. The stability of [M(II)(MeL(a))](2+)-complexes is low. In comparison to the parent 1,4-diazepan-6-amine (L(a)), it is only slightly enhanced. In analogy to L(a), MeL(a) exhibited a pronounced tendency for forming protonated species such as [M(II)(HMeL(a))](3+) or [M(II)(MeL(a))(HMeL(a))](3+) (see 6 as an example). In contrast to MeL(a), Me(3)tach forms [M(II)L](2+) complexes (M = Cu, Zn) of very high stability, and the coordination behavior corresponds mainly to an "all-or-nothing" process. Molecular mechanics calculations showed that the low stability of L(a) and MeL(a) complexes is mainly due to a large amount of torsional strain within the pure chair conformation of the diazepane ring, required for tridentate coordination. This behavior is quite contrary to Me(3)tach and tacn (tacn =1,4,7-triazacyclononane), where the main portion of strain is already preformed in the free ligand, and the amount, generated upon complex formation, is comparably low.     

Excited-state intermolecular proton transfer of firefly luciferin III. Proton transfer to a mild base

Steady-state and time-resolved techniques were employed to study the excited-state proton transfer (ESPT) from d-luciferin, the natural substrate of the firefly luciferase, to the mild acetate base in aqueous solutions. We found that in 1 M aqueous solutions of acetate or higher, a proton transfer (PT) process to the acetate takes place within 30 ps in both H(2)O and D(2)O solutions. The time-resolved emission signal is composed of three components. We found that the short-time component decay time is 300 and 600 fs in H(2)O and D(2)O, respectively. This component is attributed either to a PT process via the shortest water bridged complex available, ROH··H(2)O··Ac(-), or to PT taking place within a contact ion pair. The second time component of 2000 and 3000 fs for H(2)O and D(2)O, respectively, is attributed to ROH* acetate complex, whose proton wire is longer by one water molecule. The decay rate of the third, long-time component is proportional to the acetate concentration. We attribute it to the diffusion-assisted reaction as well as to PT process to the solvent.     

Bestimmung der Harns?ure und der Xanthinbasen im Harn

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Picosecond proton ejection: an ultrafast pH jump

The rates of proton ejection from 2-naphthol-3,6-disulfonate (pK^* = 0.5 ± 0.1) and 8-hydroxy 1,3,6-pyrene trisulfonate (pK^* = 0.4 ± 0.1) have been found to be 3.1 × 10¹⁰ s^?1 and 3.2 × 10¹⁰ s^?1, respectively. This is in keeping with the scaling of the ejection rate inversely with the excited state pK^*.     

Die forensische Untersuchung von Blutflecken

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Zweifach transitive,auflösbare Permutationsgruppen

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Isometrien von Vektorräumen. II

Ohne ZusammenfassungMeinem verehrten Lehrer Helmut Wielandt zum 70. Geburtstag