The Sgraffito and Champlevé Ceramics from Ḫirbat al-Minya at the Sea of Galilee

Die vorliegende Magisterarbeit ist eine Auswertung der glasierten Keramikfunde vom Typ der Sgraffito- und Champlevé-Waren aus Ḫirbat al-Minya am See Genezareth dar. Die kastellartige Anlage von Ḫirbat al-Minya zählt zum Typus der sogenannten Wüstenschlösser, einer Gruppe ländlicher Residenzen, die unter den Umayyaden im 7. bis 8. Jahrhundert in Syrien und Palästina entstanden sind. Bei den Ausgrabungen durch deutsche Archäologen in den 1930er Jahren wurden große Mengen an Keramik geborgen, von denen ein Teil, zusammen mit weiteren Kleinfunden, in das Berliner Museum für Islamische Kunst gelangten, wo sie jedoch nicht mehr einer abschließenden Grabungsauswertung unterzogen werden konnten. Dabei deuten besonders die Funde an glasierter Keramik auf eine Besiedlung von Ḫirbat al-Minya auch in nachummayyadischer Zeit hin. Die vorliegende Auswertung des Berliner Bestandes an Sgraffito und Champlevé-Ware, die neben schlickerbemalter Ware den Großteil am glasierten Keramik-Korpus ausmacht, ermöglicht somit einerseits Rückschlüsse auf eine relativ chronologische mittelalterliche Besiedlung von Ḫirbat al-Minya. Andererseits wird durch die Auswertung eine Vergleichsbasis für andere Fundorte im Großraum Syrien (Bilād aš-Šām) vorgelegt, wo die Auswertung glasierter Gebrauchskeramik gegenüber den sogenannten Luxuswaren lange Zeit vernachlässigt wurde.The thesis presents the glazed ceramic findings of the Sgraffito and Champlevé type from the ruin Ḫirbat al-Minya at the Sea of Galilee in present-day Israel. The ruin belongs to a number of rural residences built under the Islamic dynasty of the Umayyads in Syria and Palestine, the so-called 'desert castles'. During the excavations carried out by German archaeologists in the 1930s vast amounts of ceramics were found, of which a considerable part together with other small finds was given to the Berlin Museum for Islamic Art. However, no final evaluation of the excavations could then be undertaken. The finds of glazed ceramics particularly suggest that Ḫirbat al-Minya was still populated in medieval times in the aftermath of the Ummayyad dynasty. The present analysis of the Berlin corpus of glazed Sgraffito and Champlevé ceramics, which together with slip-painted wares forms the bulk of glazed ceramics found, makes it possible to draw conclusions for a relative dating of the medieval settlement at Ḫirbat al-Minya. Furthermore, the analysis forms a point of comparative reference for other find spots in Greater Syria (Bilād aš-Šām), where the analysis of glazed domestic wares has been much neglected in favour of so-called luxury wares

Strong and Anisotropic Superexchange in the Single-Molecule Magnet (SMM) [(Mn6OsIII)-Os-III](3+): Promoting SMM Behavior through 3d-5d Transition Metal Substitution

Höke V, Stammler A, Bögge H, Schnack J, Glaser T. Strong and Anisotropic Superexchange in the Single-Molecule Magnet (SMM) [(Mn6OsIII)-Os-III](3+): Promoting SMM Behavior through 3d-5d Transition Metal Substitution. Inorganic Chemistry. 2014;53(1):257-268.The reaction of the in situ generated trinuclear triplesalen complex [(talen(t-Bu2))Mn-3(III)(solv)(n)](3+) with (Ph4P)(3)[Os-III(CN)(6)] and NaClO4 center dot H2O affords [(Mn6OsIII)-Os-III] (ClO4)(3) (= [{(talen(t-Bu2))Mn-3(III)}(2){Os-III(CN)(6)}](ClO4)(3)) in the presence of the oxidizing agent [(tacn)(2)Ni-III] (ClO4)(3) (tacn =1,4,7-triazacyclononane), while the reaction of [(talen(t-Bu2))-Mn-3(III)(solv)(n)](3+) with K-4[Os-II(CN)(6)] and NaClO4 center dot H2O yields [(Mn6OsII)-Os-III](ClO4)(2) under an argon atmosphere. The molecular structure of [(Mn6OsIII)-Os-III](3+) as determined by single-crystal X-ray diffraction is closely related to the already published [(Mn6Mc)-M-III](3+) complexes (M-c = Cr-III, Fe-III, Co-III, Mn-III). The half-wave potential of the Os-III/Os-II couple is E-1/2 = 0.07 V vs Fc(+)/Fc. The FT-IR and electronic absorption spectra of [(Mn6OsII)-Os-III](2+) and [(Mn6OsIII)-Os-III](3+) exhibit distinct features of dicationic and tricationic [(Mn6Mc)-M-III](n+) complexes, respectively. The dc magnetic data (mu(eff) vs T, M vs B, and VTVH) of [(Mn6OsII)-Os-III](2+) are successfully simulated by a full-matrix diagonalization of a spin-Hamiltonian including isotropic exchange, zero-field splitting with full consideration of the relative orientation of the D-tensors, and Zeeman interaction, indicating antiferromagnetic Mn-III-Mn-III interactions within the trinuclear triplesalen subunits (J(Mn-Mn)((1)) = -(0.53 +/- 0.01) cm(-1), (H) over cap (ex) = -2 Sigma(i(i)center dot(S) over cap (j)) as well as across the central Os-II ion (J(Mn-Mn)((2,cis)) = -(0.06 +/- 0.01) cm(-1), (J(Mn-Mn)((2,trans)) = -(0.15 +/- 0.01) cm(-1)), while D-Mn = -(3.9 +/- 0.1) cm(-1). The mu(eff) vs T data of [(Mn6OsIII)-Os-III](3+) are excellently reproduced assuming an anisotropic Ising-like Os-III-Mn-III superexchange with a nonzero component J(Os-Mn)((aniso)) = -(11.0 +/- 1.0) cm(-1) along the Os-Mn direction, while J(Mn-Mn) = -(0.9 +/- 0.1) cm(-1) and D-Mn = -(3.0 +/- 1.0) cm(-1). Alternating current measurements indicate a slower relaxation of the magnetization in the SMM [(Mn6OsIII)-Os-III](3+) compared to the 3d analogue [(Mn6FeIII)-Fe-III](3+) due to the stronger and anisotropic M-c-Mn-III exchange interaction