Subphthalocyanine-Stoppered [2]Rotaxanes:Synthesis and Size/Energy Threshold of Slippage

Subphthalocyanine (SubPc)-stoppered [2]rotaxanes were synthesized for the first time. The rotaxane bearing unsubstituted SubPc as a stopper exhibited an equilibrium of slipping-on and slipping-off, whereas a perfluorinated SubPc stopper completely blocked slippage of the ring due to its slightly larger size. Kinetic studies revealed the Gibbs free energy of activation for the slipping-on and slipping-off processes. The optical properties of the rotaxanes, including photoinduced electron transfer, were also revealed.</p

Tricarbonyliron(0) complexes of bio-derived η4 cyclohexadiene ligands: An approach to analogues of oseltamivir

We have prepared novel [η4] and [η5]+ tricarbonyliron complexes from an unusual enantiopure cyclohexadiene ligand that possesses a quaternary stereocentre; this in turn is prepared through biotransformation of an aromatic ring. The cyclohexadiene ligand initially possessed two hydroxyl groups, both of which could be substituted with other functionality by means of an overall [η4] → [η5]+ → [η4] → [η5]+ → [η4] sequence. From six novel tricarbonyliron complexes which have been prepared, three have been characterised by x-ray crystallography. The reaction sequence we describe is potentially of relevance to the synthesis of analogues of the anti-influenza drug oseltamivir. In addition, the failure of an attempted addition of a bulky nitrogen nucleophile to an [η5]+ complex sheds light on the limits of reactivity for such additions. Thus, two bulky nucleophiles which are each known to add successfully to unencumbered [η5]+ complexes seemingly cannot be added sequentially to adjacent positions on the cyclohexadiene ligand

Directed Molecular Stacking for Engineered Fluorescent Three-Dimensional Reduced Graphene Oxide and Coronene Frameworks

[EN] Three‐dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene‐like domains present in the in situ‐formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free‐base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso‐ and β‐positions were employed in turn to act as directing entities for the assembly of new graphene‐based and foam‐like frameworks and of their corresponding coronene‐based hybrids. Investigations in the dispersed phase and in thin‐film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi‐empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the “molecular glue”. Single crystal X‐ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter‐planar distance between the rGO, coronene or graphene sheets. The host‐guest chemistry involves the porphyrins acting as guests held through π‐π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π‐conjugated molecules and materials and their π‐stacks may be relevant towards selective separation membranes, water purification and biosensing applications.S.I.P. and S.W.B. thank The Royal Society and STFC for funding. B.Y.M. thanks the University of Bath for a studentship (ORS). D.G.C. thanks the Fundación General CSIC for funding (ComFuturo Program). Dr. Jose A. Ribeiro Martins, Professors Jeremy K. M. Sanders and Paul Raithby are acknowledged for training, helpful discussions and porphyrin supramolecular chemistry. The S.I.P. group thanks the EPSRC for funding to the Centre of Graphene Science (EP/K017160/1) and to the Centre for Doctoral Training in Sustainable Chemical Technologies (EP/L016354/1). The authors thank EPSRC National Service for Mass Spectrometry at Swansea and EPSRC National Service for Crystallography at Southampton for data collection. The authors also acknowledge the ERC for the Consolidator Grant O2SENSE (617107, 2014–2019)

Monoclinic modification of 1,1,3,3,5,5-hexa­methyl-cyclo-1,3,5-tris­tannathiane

The asymmetric unit of the title compound, [Sn3(CH3)6S3], contains two molecules with twist-boat conformations. There are intermolecular S⋯H (2.929 Å), S⋯S (3.433 Å), S⋯C (3.465 Å) and C⋯H (2.898 Å) inter­actions in addition to prominent intermolecular Sn⋯S inter­actions of 3.692 and 3.769 Å

Ruthenium catalyzed remote C4-selective C–H functionalisation of carbazoles via σ-activation

We report the C4-selective C–H alkylation of carbazole derivatives furnished with a pyrimidine directing group at N9. This was realized using ruthenium catalyzed r-activation methodology, whereby C–H activation at C1 enables the interaction of this ruthenacycle, at the para position to the metal center, with tertiary alkyl radical

(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

The 3:2 Charge Transfer (CT) co-crystal (Perylene)3(TCNQF1)2 is grown by the Physical Vapor Transport (PVT) method, and characterized structurally and spectroscopically. Infrared analysis of the charge sensitive modes reveals a low degree of charge transfer (less than 0.1) between donor and acceptor molecules. The crystal is isostructural to the other 3:2 CT crystals formed by Perylene with TCNQF2 and TCNQF4, whereas such stoichiometry and packing is not known for the CT crystals with non-fluorinated TCNQ. The analysis of the isostructural family of 3:2 Perylene–TCNQFx (x = 1,2,4) co-crystal put in evidence the role of weak F…HC bonding in stabilizing this type of structure</jats:p

Effect of Benzoic Acids on Barite and Calcite Precipitation

The effect of various benzoic acids on the precipitation of barite (BaSO4) and calcite (CaCO3) was investigated. The acids varied in the number of carboxylate groups, from dibenzoic acids (phthalic, isophthalic, and terephthalic) through to the hexabenzoic acid (mellitic acid). It was found that the stereochemistry of the dibenzoic acids was important, as was the pH of the solution (trimesic acid was used as a test case and showed that greatest inhibition was achieved with all carboxylate groups deprotonated). Interestingly, for both the calcite and barite systems, mellitic acid was found to be both a potent inhibitor and a significant crystal growth modifier. In the case of barite, the presence of mellitic acid produced nanoparticles that agglomerated. The nanoparticles were found to be 20 nm in size from X-ray diffraction (XRD) line width analysis and 20-50 nm from transmission electron microscopy (TEM). Humic acid was also tested and found to form bundled fibers of barium sulfate

Chiral Phthalocyanines through Axial Coordination

A novel approach to axially induce chirality on silicon phthalocyanines via a microwave-assisted route is reported. CD analysis provides spectroscopic evidence that chirality is transferred onto both Soret and Q-bands of the phthalocyanine core. A chiral naphthalenediimide ligand was found to induce the largest Cotton effect on the macrocycle absorptions