Chronopotentiometric determination of the outer-sphere association constants of substitution-inert metal complexes

Summary A new method for the determination of association constants by the measurement of chronopotentiometric transition time has been developed and applied to the study on the outer-sphere association of some substitution-inert complex cations with sulphate ions. The association constants were determined from the change in transition time as function of the concentration of sulphate ions at ionic strength 0.1 (NaClO₄) and 25° C: 93 ±8 for [Co(NH₃)₆]³⁺SO₄ ^2–, 99 ±15 for [Co(en)₃]³⁺SO₄ ^2–, 61 ±7 for [Cr(NH₃)₆]³⁺SO₄ ^2– and 58 ±8 for [Cr(en)₃]³⁺SO₄ ^2–. The ratios of the diffusion coefficients of the univalent ion-pairs and tervalent substitution-inert complex cations were also obtained. From these ratios the diffusion coefficients of the univalent ion-pairs were calculated, which were found to differ not greatly from those of univalent complex ions with similar structures.

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Zusammenfassung Eine neue Methode zur Bestimmung von Assoziationskonstanten aus den Transitionszeiten chronopotentiometrischer Messungen wurde entwickelt. Sie wurde zur Untersuchung der Assoziation von Sulfationen in zweiter Sphäre an koordinativ abgesättigten Komplex-Kationen herangezogen. Die Assoziationskonstanten wurden aus der Abhängigkeit der Transitionszeit von der Sulfatkonzentration in Medien der Ionenstärke 0,1 (NaClO₄) und bei 25° C bestimmt. Man erhält folgende Werte: 93±8 für [Co(NH₃)₆]³⁺SO₄ ^2–, 99±15 für [Co(en)₃]³⁺SO₄ ^2–, 61±7 für [Cr(NH₃)₆]³⁺SO₄ ^2– und 58±8 für [Cr(en)₃]³⁺SO₄ ^2–. Die Verhältnisse der Diffusionskoeffizienten der einwertigen Ionenpaare zu denen der dreiwertigen Komplex-Kationen wurden ebenfalls bestimmt. Aus diesen Verhältnissen lassen sich die Diffusionskoeffizienten der Ionenpaare berechnen. Man erhält eine gute Übereinstimmung mit den Werten für einwertige Komplexionen mit ähnlicher Struktur.

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Dedicated to Prof. Dr. M. von Stackelberg on his 70th birthday.     

Freie Diffusion in einem Zweikomponenten-System, in dem Volumen?nderung beim Mischen eintritt

Ohne Zusammenfassung     

Fine structure in the energy region of the isoscalar giant quadrupole resonance: characteristic scales from a wavelet analysis

Fine structure in the energy region of the isoscalar giant quadrupole resonance in nuclei is observed in high-resolution proton scattering experiments at iThemba LABS over a wide mass range. A novel method based on wavelet transforms is introduced for the extraction of scales characterizing the fine structure. A comparison with microscopic model calculations including two-particle two-hole (2p2h) degrees of freedom identifies the coupling to surface vibrations as the main source of the observed scales. A generic pattern is also found for the stochastic coupling to the background of the more complex states.     

Thermal splitting of Bis-Cu(II) octaphyrin(1.1.1.1.1.1.1.1) into two Cu(II) porphyrins

When heated, bis-Cu(II) octaphyrin(1.1.1.1.1.1.1.1) is quantitatively split into two Cu(II) porphyrins both in solution and film states, which is accompanied by large absorption spectral changes.     

Resonance effects on coherent phonon generation in lead phthalocyanine crystalline films

We report the first observation of coherent phonons in crystalline lead phthalocyanine (PbPc) films grown on a (0001) sapphire substrate by using a pump–probe technique. Coherent phonon oscillations corresponding to intermolecular (lattice) vibrations in the PbPc film are observed in the frequency region from 1 to 5 THz. It is found that the intensities of coherent phonons are resonantly enhanced at the exciton energies of the Q band observed in the absorption spectrum. PACS 78.47.+p; 78.66.-w; 82.53.Xa; 78.40.Me     

Proton-sensitive fluorescent organogels

A 1,10-phenanthroline-appended cholesterol-based gelator (1) and its nongelling reference compound (2) were synthesized. Among 19 solvents tested herein, gelator 1 could gelate 11 solvents including alcohols, dipolar aprotic solvents, organic acids and a base (triethylamine), indicating that 1 acts as a versatile gelator. The TEM observation gave a visual image showing that fibrillar aggregates are entangled in the three-dimensional network structure. In the fluorescence measurements, most gels afforded an emission maximum at 394 nm (purple emission), whereas only the acetic acid gel afforded an emission maximum at 522 nm (yellow emission). Thus, the influence of protonation of the 1,10-phenanthroline nitrogens (by trifluoroacetic acid) on the fluorescence properties in the gel phase was investigated in detail. The results have established that the fluorescence intensity of 1 x H+ becomes particularly strong in the gel phase, presumably because of the energy transfer from neutral 1* to protonated 1 x H+ and the restriction of the 1 x H+ molecular motion. The finding suggests the possibility that the gel system would be useful not only as a new proton-sensitive fluorescence system but also as a new medium for designing efficient energy transfer systems.