Morphological control of heteroleptic cis- and trans-Pd2L2Lʹ2 cages

Control over the integrative self-sorting of metallo-supramolecular assemblies has recently generated significant interest as it opens up possibilities of introducing increased complexity and function into a single self-assembled architecture. Here, the relationship between the geometry of three ligand components and morphology of three self-sorted heteroleptic [Pd2L2Lʹ2]4+ cages is examined. Pd-mediated assembly of two bis-monodentate pyridyl ligands with native bite angles of 75° and 120° affords a cis-[Pd2L2Lʹ2]4+ cage while the same reaction with two ligands bearing bite angles of 75° and 60° forces an anti-conformation for latter ligand, leading to an unprecedented, self-penetrating structural motif; a trans-[Pd2(anti-L)2Lʹ2]4+ heteroleptic cage bearing a “doubly-bridged figure-eight” topology. Each heteroleptic assembly can be accessed through cage-to-cage conversion of their homoleptic precursors, and notably, morphological control of [Pd2L2Lʹ2] cages is achieved through selective ligand displacement transformations in a system of three ligands and at least six possible cage products

Mechanistic Interplay between Light Switching and Guest Binding in Photochromic [Pd 2 Dithienylethene 4 ] Coordination Cages

Photochromic [Pd2L4] coordination cages based on dithienylethene (DTE) ligands L allow triggering guest uptake and release by irradiation with light of different wavelengths. The process involves four consecutive electrocyclic reactions to convert all chromophores between their open and closed photoisomeric forms. So far, guest affinity of the fully switched species was elucidated, but mechanistic details concerning the intermediate steps remained elusive. Now, a new member of the DTE cage family allows unprecedented insight into the interplay between photoisomerization steps and guest location inside/outside the cavity. Therefore, the intrinsic chirality of the DTE backbones was used as reporter for monitoring the fate of a chiral guest. In its "open" photoisomeric form (o-L, [Pd2(o-L)4] = o-C), the C2-symmetric DTE chromophore quickly converts between energetically degenerate P and M helical conformations. After binding homochiral 1R-(-) or 1S-(+) camphor sulfonate (R-CSA or S-CSA), guest-to-host chirality transfer was observed via a circular dichroism (CD) signal for the cage-centered absorption. Irradiating the R/S-CSA@o-C host-guest complexes at 313 nm produced configurationally stable "closed" photoisomers, thus locking the induced chirality with an enantiomeric excess close to 25%. This value (corresponding to chiral induction for one out of four ligands), together with DOSY NMR, ion mobility mass spectrometry, and X-ray structure results, shows that closure of the first photoswitch is sufficient to expel the guest from the cavity

Ferrocene derivatives of liquid chiral molecules allow assignment of absolute configuration by X-ray crystallography

The present study investigates a synthetically simple ferrocene derivatization of natural products and active pharmaceutical ingredients. Seven new crystal structures are analyzed together with 16 structures of ferrocene derivatives reported previously. In all cases, the unambiguous determination of the absolute structure was established from anomalous dispersion using the methods of Flack and Parsons. A comparison with other derivatization approaches shows the advantage of the described ferrocene derivatization for establishing the absolute configuration of novel compounds

Rice field flora and vegetation in the provinces of Valencia and Tarragona

Twenty nine emergent and twenty floating or submerged taxa , were found in the rice fields in Valencia and Tarragona provinces. Eleven of the se taxa, all them emergent, are alien Of introduced ones. Echinochloa oryzoides and E. oryzicola are the most important in both areas, together with Cyperus difformis and Echinochloa hispidula in Valencia. The remaining thirty eight taxa belong to the native flora. There are predominantly the emergent Scirpus maritimus, Alisma plantago-aquatica. Echinochloa crus-galli and Paspalum distichum; the floating Lemna minor and L. gibba; the submersed Potamogeton nodosus; Zannichellia palustris and Najas minor; and the macroscopical algae Chara vulgaris, Cladophora glomerata, Oedogonium capilliforme, Spirogyra spp., Pithophora oedogania and Hydrodictyon reticulatum. The flora evolution during the last years is analyzed and the present weed communities are studied. The contribution of the different phytosociological classes to the rice field weed flora is presented.De los 49 táxones registrados (29 emergentes y 20 flotantes o sumergidos) 11 son exóticos introducidos, de los cuales los más importantes son Echinochloa oryzoides y E. oryzicolaen ambas zonas, además de Cyperus difformis y Echinochloa hispidula en Valencia, y el resto propios de la flora autóctona, predominando Scirpus maritimus, Alisma plantago-aquatica. Echinochloa crus-galli y Paspalum distichum como emergentes, Lemna minor y L. gibba como flotantes, Potamogeton nodosus, Zannichellia palustris y Najas minor como sumergidos y Chara vulgaris, Cladophora glomerata, Oedogonium capilliforme. Spirogyra spp., Pirhophora oedogonia e Hydrodictyon reticulatum como algas macroscópicas. Se analiza la evolución experimentada por la flora en los últimos años, además de estudiar las comunidades vegetales presentes y de indicar la importancia de las distintas clases fitosociológicas en su contribución a la flora arvense del cultivo

Additive Anti-Tumor Effects of Lovastatin and Everolimus In Vitro through Simultaneous Inhibition of Signaling Pathways

This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are creditedThis work was supported by a research grant from the Ludwig-Maximilians University of Munich (Förderprogramm für Forschung und Lehre [FöFoLe], grant number 865/829)

Two-stage directed self-assembly of a cyclic [3]catenane.

Interlocked molecules possess properties and functions that depend upon their intricate connectivity. In addition to the topologically trivial rotaxanes, whose structures may be captured by a planar graph, the topologically non-trivial knots and catenanes represent some of chemistry's most challenging synthetic targets because of the three-dimensional assembly necessary for their construction. Here we report the synthesis of a cyclic [3]catenane, which consists of three mutually interpenetrating rings, via an unusual synthetic route. Five distinct building blocks self-assemble into a heteroleptic triangular framework composed of two joined Fe(II)3L3 circular helicates. Subcomponent exchange then enables specific points in the framework to be linked together to generate the cyclic [3]catenane product. Our method represents an advance both in the intricacy of the metal-templated self-assembly procedure and in the use of selective imine exchange to generate a topologically complex product.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC) and a Marie Curie fellowship for J.J.H. (ITN-2010–264645). The authors thank the Diamond Light Source (UK) for synchrotron beamtime on I19 (MT7984 and MT8464).This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.220

DSR: enhanced modelling and refinement of disordered structures with SHELXL

One of the remaining challenges in single-crystal structure refinement is the proper description of disorder in crystal structures. This paper describes a computer program that performs semi-automatic modelling of disordered moieties in SHELXL [Sheldrick (2015). Acta Cryst. C71, 3–8.]. The new program contains a database that includes molecular fragments and their corresponding stereochemical restraints, and a placement procedure to place these fragments on the desired position in the unit cell. The program is also suitable for speeding up model building of well ordered crystal structures.peerReviewe

Ferrocene derivatives of liquid chiral molecules allow for absolute structure determination by X-ray crystallography

The present study investigates a synthetically simple ferrocene derivatization of natural products and active pharmaceutical ingredients. Seven new crystal structures are analyzed together with 16 structures of ferrocene derivatives reported previously. In all cases the unambiguous determination of the absolute structure was established from anomalous dispersion using the methods of Flack, Hooft and Parsons. A comparison with other derivatization approaches shows the advantage of the herein described ferrocene derivatization for establishing the absolute configuration of novel compounds

Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by Pd II Coordination Sphere Engineering

For metal‐mediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a non‐statistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of square‐planar PdII cations and bis‐monodentate nitrogen donor ligands allows to control the size and shape of the assembled product, from [Pd2L4] cages over [Pd2L3] bowl‐shaped structures to [Pd2L2] rings. Therefore, banana‐shaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C60 and C70 fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal X‐ray diffraction. The three cages based on pyridine, 6‐quinoline or 3‐quinoline donors were found to either bind C60, C70 or no fullerene at al

A Charge-Neutral Self-Assembled L₂Zn₂ Helicate as Bench-Stable Receptor for Anion Recognition at Nanomolar Concentration

The field of anion recognition chemistry is dominated by two fundamental approaches to design receptors. One relies on the formation of covalent bonds resulting in organic and often neutral host species, while the other one utilizes metal-driven self-assembly for the formation of charged receptors with well-defined nanocavities. Yet, the combination of their individual advantages in the form of charge-neutral metal-assembled bench-stable anion receptors is severely lacking. Herein, we present a fluorescent and uncharged double-stranded hydroxyquinoline-based zinc(II) helicate with the ability to bind environmentally relevant dicarboxylate anions with high fidelity in dimethyl sulfoxide (DMSO) at nanomolar concentrations. These dianions are pinned between zinc(II) centers with binding constants up to 145 000 000 M–1. The presented investigation exemplifies a pathway to bridge the two design approaches and combine their strength in one structural motif as an efficient anion receptor