Supramolecular coordination chemistry: the synergistic effect of serendipity and rational design

Supramolecular coordination compounds bear exceptional advantages over their organic counterparts. They are available in one-pot reactions and in high yields and display physical properties that are generally inaccessible with organic species. Moreover, their weak, reversible, noncovalent bonding interactions facilitate error checking and self-correction. This Review emphasizes the achievements in supramolecular coordination chemistry initiated by serendipity and their materialization based on rational design. The recognition of similarities in the synthesis of different supramolecular assemblies allows prediction of potential results in related cases. Supramolecular synthesis obeys guidelines comparable to the "lead sheet" used by small jazz ensembles for improvisation and therefore more often leads to unpredicted results. The combination of detailed symmetry considerations with the basic rules of coordination chemistry has only recently allowed for the design of rational strategies for the construction of a variety of nanosized systems with specified size and shape.     

Strain induced epitaxial relationships of Cr on Co/Pd(111)

The growth and structure of Co ultra-thin films on Pd(111) and Cr on Co/Pd(111) have been analyzed by grazing incidence X-ray diffraction and low energy electron diffraction. It is shown that the in-plane lattice constant of the epitaxial Co film depends on the growth temperature. Although the strain decreases as a function of the Co film thickness, it persists for 20 monolayer (ML) films or even thicker. When Cr is deposited at room temperature on a strained Co film (10 to 20 ML thick) a Kurdjumov–Sachs epitaxial relationship is observed, whereas when Cr is deposited on a Co(0001) single-crystal or on a very thick Co film on Pd(111), a Nishyama–Wassermann orientation is obtained.     

38. Symposium für Theoretische Chemie

Das 38. Symposium für Theoretische Chemie fand Ende August an der International University of Bremen (IUB) statt. 15 Hauptvorträge, 15 Kurzvorträge und 90 Poster boten den 160 Teilnehmern eine Mischung aus Methodenentwicklung und Anwendung sowohl in der Quantenchemie als auch in der Dynamik molekularer Prozesse.     

Uranium-mediated reductive conversion of CO(2) to CO and carbonate in a single-vessel, closed synthetic cycle

The new neopentyl (Neop)-substituted tris(aryloxide) U(iii) complex [(((Neop,Me)ArO)(3)tacn)U(III)] reacts with CO(2) to form CO and the bridging carbonate complex [{(((Neop,Me)ArO)(3)tacn)U(IV)}(2)(μ-CO(3))]. The uranium(iv) bridging oxo [{(((Neop,Me)ArO)(3)tacn)U(IV)}(2)(μ-O)] has been determined to be the intermediate in this reaction. For the first time, both U(iv) complexes can be reduced back to the U(iii) starting material. Thus, with KC(8) as reductant, [(((Neop,Me)ArO)(3)tacn)U(III)] engages in a synthetic cycle, in which CO(2) is converted to CO and CO(3)(2-).     

Synthesis,Magnetic Properties,and STM Spectroscopy of Cobalt(II) Cubanes [CoII4(Cl)4(HL)4]

Reaction of cobalt(II) chloride hexahydrate with N‐substituted diethanolamines H₂L^2–4 ( 3 ) in the presence of LiH in anhydrous THF leads under anaerobic conditions to the formation of three isostructural tetranuclear cobalt(II) complexes [Co^II₄(Cl)₄(HL^2–4)₄] ( 4 ) with a [Co₄(μ₃‐O)₄]⁴⁺ cubane core. According to X‐ray structural analyses, the complexes 4 a , c crystallize in the tetragonal space group I4₁/a, whereas for complex 4 b the tetragonal space group P$\bar 4$ was found. In the solid state the orientation of the cubane cores and the formation of a 3D framework were controlled by the ligand substituents of the cobalt(II) cubanes 4 . This also allowed detailed magnetic investigations on single crystals. The analysis of the SQUID magnetic susceptibility data for 4 a gave intramolecular ferromagnetic couplings of the cobalt(II) ions (J₁≈20.4 K, J₂≈7.6 K), resulting in an S=6 ground‐state multiplet. The anisotropy was found to be of the easy‐axis type (D=?1.55 K) with a resulting anisotropy barrier of Δ≈55.8 K. Two‐dimensional electron‐gas (2DEG) Hall magnetization measurements revealed that complex 4 a is a single‐molecule magnet and shows hysteretic magnetization characteristics with typical temperature and sweep‐rate dependencies below a blocking temperature of about 4.4 K. The hysteresis loops collapse at zero field owing to fast quantum tunneling of the magnetization (QTM). The structural and electronic properties of cobalt(II) cubane 4 a , deposited on a highly oriented pyrolytic graphite (HOPG) surface, were investigated by means of STM and current imaging tunneling spectroscopy (CITS) at RT and standard atmospheric pressure. In CITS measurements the rather large contrast found at the expected locations of the metal centers of the molecules indicated the presence of a strongly localized LUMO.     

The challenge of analyzing beta-blocker drugs in sludge and wastewater

In this study, different approaches were used to assess and overcome the severe effects of interference from the sample matrix from different types of sludges and wastewater on the analysis of nine beta-blockers and the beta sympathomimetic clenbuterol. The partitioning of the target compounds into sludge was investigated in wastewater treatment plants (WWTPs) in both Canada and Germany to evaluate whether this is an important mechanism for removal from sewage. Due to ion suppression in the electro spray interface, absolute recoveries were for certain compounds even lower than 20%. By using surrogate standards, acceptable relative recoveries of >75% were achieved for WWTP influents and effluents and for sludges. These matrix effects underline the need to use appropriate surrogate standards to aid in analyte quantitation. Using the developed methods, beta-blockers were detected at concentrations up to 2 μg/L in WWTP effluents, with metoprolol, sotalol, and atenolol present as the dominant compounds. Removal rates within WWTPs were highly inconsistent and ranged from 1-69%. Propranolol showed the greatest degree of partitioning into sludge with solid/water partition coefficients of one order of magnitude higher than those for all other compounds. However, even for propranolol, sorption did not contribute significantly to the overall elimination in WWTPs. It is likely that the removal of beta-blockers during waste water treatment can be attributed primarily to microbial biodegradation.     

Electronic structure study by means of x-ray spectroscopy and theoretical calculations of the "ferric star" single molecule magnet

The electronic structure of the single molecule magnet system {M[Fe(L(1))(2)](3)}4CHCl(3) [M=Fe,Cr;L(1)=CH(3)N(CH(2)CH(2)O)(2) (2-)] has been studied using x-ray photoelectron spectroscopy, x-ray-absorption spectroscopy, soft-x-ray emission spectroscopy, as well as theoretical density-functional-based methods. There is a good agreement between theoretical calculations and experimental data. The valence band mainly consists of three bands between 2 and 30 eV. Both theory and experiments show that the top of the valence band is dominated by the hybridization between Fe 3d and O 2p bands. From the shape of the Fe 2p spectra it is argued that Fe in the molecule is most likely in the 2+ charge state. Its neighboring atoms (O,N) exhibit a magnetic polarization yielding effective spin S=52 per iron atom, giving a high-spin state molecule with a total S=5 effective spin for the case of M=Fe.     

Magneto-optical interactions in single-molecule magnets: Low-temperature photon-induced demagnetization

We show that the irradiation of SMM molecules at optical wavelengths can drive an increase or a decrease of the magnetic moment of a SMM, even though the energy of the photons does not correspond to a precise electronic or spin transition, the light pulse triggering a phonon-assisted spin transition. The process is sensitive to the power of the incident light. This result most probably explains why it has been so far impossible to observe the opening of the hysteresis loop on thin films of SMM with the XMCD technique. The consequences of these observations are manifold: they bring a means of controlling molecular magnets, open prospects in the field of quantum computing, and may enable the realization of coherent microwave sources through stimulated superradiance.