Size-determining dependencies in supramolecular organometallic host-guest chemistry

Treatment of the pentaphosphaferrocene [Cp*Fe(η⁵‐P₅)] with Cu^I halides in the presence of different templates leads to novel fullerene‐like spherical molecules that serve as hosts for the templates. If ferrocene is used as the template the 80‐vertex ball [Cp₂Fe]@[{Cp*Fe(η⁵‐P₅)}₁₂{CuCl}₂₀] ( 4 ), with an overall icosahedral C₈₀ topological symmetry, is obtained. This result shows the ability of ferrocene to compete successfully with the internal template of the reaction system [Cp*Fe(η⁵‐P₅)], although the 90‐vertex ball [{Cp*Fe(η⁵:η¹:η¹:η¹:η¹:η¹‐P₅)}₁₂(CuCl)₁₀(Cu₂Cl₃)₅{Cu(CH₃CN)₂}₅] ( 2 a ) containing pentaphosphaferrocene as a guest is also formed as a byproduct. With use of the triple‐decker sandwich complex [(CpCr)₂(μ,η⁵‐As₅)] as a template the reaction between [Cp*Fe(η⁵‐P₅)] and CuBr leads to the 90‐vertex ball [(CpCr)₂(μ,η⁵‐As₅)]@[{Cp*Fe(η⁵‐P₅)}₁₂{CuBr}₁₀{Cu₂Br₃}₅{Cu(CH₃CN)₂}₅] ( 6 ), in which the complete molecule acts as a template. However, if the corresponding reaction is instead carried out with CuCl, cleavage of the triple‐decker complex is found and the 80‐vertex ball [CpCr(η⁵‐As₅)]@[{Cp*Fe(η⁵‐P₅)}₁₂{CuCl}₂₀] ( 5 ) is obtained. This accommodates as its guest [CpCr(η⁵‐As₅)], which has only 16 valence electrons in a triplet ground state and is not known as a free molecule. The triple‐decker sandwich complex [(CpCr)₂(μ,η⁵‐As₅)] requires 53.1 kcal mol^?1 to undergo cleavage (as calculated by DFT methods) and therefore this reaction is clearly endothermic. All new products have been characterized by single‐crystal X‐ray crystallography. A favoured orientation of the guest molecules inside the host cages has been identified, which shows π???π stacking of the five‐membered rings (Cp and cyclo‐As₅) of the guests and the cyclo‐P₅ rings of the nanoballs of the hosts.     

Application of spatially and temporally apodized non-confocal acoustic transmission microscopy to imaging of directly bonded wafers

Application of a line-shaped point spread function (PSF) to imaging of void defects in directly bonded wafers is considered. Two non-confocally adjusted spherical transducers are employed to implement an acoustic microscope operating in transmission with a time dependent point spread function, whose shape is optimized by both temporal apodization of the received signal and spatial apodization of the transducer aperture. Strong imaging artifacts resulting from the generation and detection of edge waves are eliminated in this way. It is shown by several examples that only a broadband system can be utilized in order to obtain a line-shaped PSF suitable for imaging.     

Combined surface-focused acoustic microscopy in transmission and scanning ultrasonic holography

Employment of ultrasound techniques in nondestructive testing may require identification of the acoustic modes contributing to imaging. Such identification can be achieved, with some restrictions, by time-of-flight analysis. Another approach is acoustic holography that reveals the propagation properties of any selected mode. In anisotropic media, the propagation features are distinct and allow for a reliable classification of the selected mode. Both techniques were applied for classification of bonded, disbonded, and weakly bonded areas in directly bonded semiconductor wafers.     

The Maxwell-Contact

In multibody systems, two alternative approaches exist to compute contact forces between bodies. The unilateral constraint contact and the unilateral regularized contact do not take into account the influence of the deformation due to other contacts on a body using rigid body dynamics. In this paper, a third alternative, i.e. the Maxwell-Contact, is derived coupling the deformations of different contacts on one body quasi-statically. An academic example validates the fundamental properties of the contact model and the application in a simulation of a pushbelt CVT shows improved results. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conformational transitions and aggregations of regioregular polyalkylthiophenes

Diverse conformational transitions and aggregations of regioregular poly (3-alkylthiophene)s (PATs) in different environment have been studied by means of AFM and UV-vis-spectroscopy. In methanol, which is a non-solvent for both alkyl side groups and aromatic backbone at low polymer concentration, PATs chains fold into compact poorly ordered flat structures. At higher polymer concentration PATs molecules undergo 3D aggregation into near spherical particles. In hexane, which is a selective solvent for alkyl side chains, PATs molecules undergo ordered main-chain collapse followed by 1D aggregation. Concentration-independent red shift of λmax and good resolved fine vibronic structure in the electronic absorption spectra indicate that planarization occurs on the single-molecule level.