Investigating the diastereoselective synthesis of a macrocycle under Curtin-Hammett control.

This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable π-conjugated materials for recognition, sensing, and optoelectronics. For the first time, we use the Curtin-Hammett principle to investigate a chiral macrocyclisation reaction, revealing the potential for supramolecular π-π interactions to direct the outcome of a dynamic kinetic resolution, favouring the opposite macrocyclic product to that expected under reversible, thermodynamically controlled conditions. Specifically, a dynamic, racemic perylene diimide dye (1 : 1  : ) is strapped with an enantiopure ()-1,1'-bi-2-naphthol group (-BINOL) to form two diastereomeric macrocyclic products, the homochiral macrocycle () and the heterochiral species ().

A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence.

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized chiral framework is conducive to directing π-π self-assembly and delivering a strong and persistent CPL signal. Here, perylene diimides (PDIs) are an excellent choice for the organic dye component because, alongside their tunable photophysical and self-assembly properties, functionalization of the PDI's core yields a twisted, chiral π-system, capable of CPL. However, configurationally stable PDI-based macrocycles are rare, and those that are also capable of π-π self-assembly beyond dimers are unprecedented, both of which are advantageous for robust self-assembled chiroptical materials.

Photoinduced radical formation in hydrogen-bonded organic frameworks.

Hydrogen-bonded organic frameworks (HOFs) constructed from naphthalene-diimide bearing tectons undergo photochromic changes whilst forming radical bearing species within the framework structure.

Donor-Acceptor Dyads and Triads Employing Core-Substituted Naphthalene Diimides: A Synthetic and Spectro (Electrochemical) Study.

Donor-acceptor dyads and triads comprising core-substituted naphthalene diimide (NDI) chromophores and either phenothiazine or phenoxazine donors are described. Synthesis combined with electrochemical and spectroelectrochemical investigations facilitates characterisation of the various redox states of these molecules, confirming the ability to combine arrays of electron donating and accepting moieties into single species that retain the redox properties of these individual moieties.

Palladium(II) -cyano-aminothiophenolate (ocap) complexes.

A series of Pd(II) complexes containing -cyano-aminothiophenolate (ocap) ligands have been prepared and their molecular structures elucidated. Hg(II) ocap complexes, [Hg{SCHXN(CN)}] (X = H, Me) (1), react with NaS to afford HgS and Na[ocap] which reacts with K[PdCl] to afford palladium ocap complexes [Pd{SCHXN(CN)}] (2). A second route to these coordination polymers has also been developed from reactions of 2-aminobenzothiazole (abt) complexes, -PdCl(abt) (3), with NaOH.

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle.

This work showcases chiral complementarity in aromatic stacking interactions as an effective tool to optimize the chiroptical and electrochemical properties of perylene diimides (PDIs). PDIs are a notable class of robust dye molecules and their rich photo- and electrochemistry and potential chirality make them ideal organic building blocks for chiral optoelectronic materials. By exploiting the new bay connectivity of twisted PDIs, a dynamic bis-PDI macrocycle (the "Pink Box") is realized in which homochiral PDI-PDI π-π stacking interactions are switched on exclusively.

Biomimics of [FeFe]-hydrogenases incorporating redox-active ligands: synthesis, redox properties and spectroelectrochemistry of diiron-dithiolate complexes with ferrocenyl-diphosphines as FeS surrogates.

[FeFe]-Ase biomimics containing a redox-active ferrocenyl diphosphine have been prepared and their ability to reduce protons and oxidise H studied, including 1,1'-bis(diphenylphosphino)ferrocene (dppf) complexes Fe(CO)(μ-dppf)(μ-S(CH)S) ( = 2, edt; = 3, pdt) and Fe(CO)(μ-dppf)(μ-SAr) (Ar = Ph, -tolyl, -CHNH), together with the more electron-rich 1,1'-bis(dicyclohexylphosphino)ferrocene (dcpf) complex Fe(CO)(μ-dcpf)(μ-pdt). Crystallographic characterisation of four of these show similar overall structures, the diphosphine spanning an elongated Fe-Fe bond ( 2.6 Å), lying to one sulfur and to the second.

The chemistry of phosphines in constrained, well-defined microenvironments.

Developments in the confinement of phosphines within micro- or nano-environments are explored. Phosphines are ubiquitous across metal coordination chemistry and underpin some of the most famous homogeneous transition metal catalysts. Constraining phosphines within confined environments influences not only their behaviour but also that of their metal complexes.