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.

Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.

Mn(diimine)(CO)X (X = halide) complexes are critical components of chromophores, photo- and electrocatalysts, and photoactive CO-releasing molecules (photoCORMs). While these entities have been incorporated into metal-organic frameworks (MOFs), a detailed understanding of the photochemical and chemical processes that occur in a permanently porous support is lacking. Here we site-isolate and study the photochemistry of a Mn(diimine)(CO)Br moiety anchored within a permanently porous MOF support, allowing for not only the photo-liberation of CO from the metal but also its escape from the MOF crystals.

How Reproducible is the Synthesis of Zr-Porphyrin Metal-Organic Frameworks? An Interlaboratory Study.

Metal-organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, a range of crystal structures can often be accessed from the same building blocks, which complicates the phase selectivity. Likewise, the high sensitivity to slight changes in synthesis conditions may cause reproducibility issues.

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.

Densified HKUST-1 Monoliths as a Route to High Volumetric and Gravimetric Hydrogen Storage Capacity.

We are currently witnessing the dawn of hydrogen (H) economy, where H will soon become a primary fuel for heating, transportation, and long-distance and long-term energy storage. Among diverse possibilities, H can be stored as a pressurized gas, a cryogenic liquid, or a solid fuel adsorption onto porous materials. Metal-organic frameworks (MOFs) have emerged as adsorbent materials with the highest theoretical H storage densities on both a volumetric and gravimetric basis.

How Reproducible are Surface Areas Calculated from the BET Equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials.

Order, disorder, and metalation of tetraphenylporphyrin (2-TPP) on Au(111).

A thermally induced order-disorder transition of tetraphenylporphyrin (2-TPP) on Au(111) is characterised by scanning probe microscopy and X-ray photoelectron spectroscopy-based techniques. We observed that a transition from an ordered close-packed phase to a disordered diffuse phase is correlated with an on-surface cyclodehydrogenation reaction, and that additional heating of this diffuse phase gives rise to a single distinct nitrogen environment indicative of the formation of a Au-TPP species.

Mechanically interlocked molecular handcuffs.

The field of mechanically interlocked molecules that employ a handcuff component are reviewed. The variety of rotaxane and catenane structures that use the handcuff motif to interlock different components are discussed and a new nomenclature, distilling diverse terminologies to a single approach, is proposed. By unifying the interpretation of this class of molecules we identify new opportunities for employing this structural unit for new architectures.

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.

Molecular dopant determines the structure of a physisorbed self-assembled molecular network.

A small percentage of an impurity was shown, via scanning tunneling microscopy, to drastically change the on-surface self-assembly behavior of an aromatic tetracarboxylic acid, by initiating the nucleation and growth of a different polymorph. Molecular modelling simulations were used to shed further light onto the dopant-controlled assembly behaviour.

Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction.

The on-surface synthesis of covalently bonded materials differs from solution-phase synthesis in several respects. The transition from a three-dimensional reaction volume to quasi-two-dimensional confinement, as is the case for on-surface synthesis, has the potential to facilitate alternative reaction pathways to those available in solution. Ullmann-type reactions, where the surface plays a role in the coupling of aryl-halide functionalised species, has been shown to facilitate extended one- and two-dimensional structures.

Porous Metal-Organic Polyhedra: Morphology, Porosity, and Guest Binding.

Designing porous materials which can selectively adsorb CO or CH is an important environmental and industrial goal which requires an understanding of the host-guest interactions involved at the atomic scale. Metal-organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs , , ), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra.

Metal-Organic Frameworks and Metal-Organic Cages - A Perspective.

The fields of metal-organic cages (MOCs) and metal-organic frameworks (MOFs) are both highly topical and continue to develop at a rapid pace. Despite clear synergies between the two fields, overlap is rarely observed. This article discusses the peculiarities and similarities of MOCs and MOFs in terms of synthetic strategies and approaches to system characterisation.

On-surface chemical reactions characterised by ultra-high resolution scanning probe microscopy.

In the last decade it has become possible to resolve the geometric structure of organic molecules with intramolecular resolution using high resolution scanning probe microscopy (SPM), and specifically using the subset of SPM known as noncontact atomic force microscopy (ncAFM). In world leading groups it has become routine not only to perform sub-molecular imaging of the chemical, electronic, and electrostatic properties of single molecules, but also to use this technique to track complex on-surface chemical reactions, investigate novel reaction products, and even synthesise new molecular structures one bond at a time. These developments represent the cutting edge of characterisation at the single chemical bond level, and have revolutionised our understanding of surface-based chemical processes.

-Alkoxy-pillar[5]arenes as Electron Donors: Electrochemical Properties of Dimethoxy-Pillar[5]arene and Its Corresponding Rotaxane.

1,4-dimethoxypillar[5]arene undergoes reversible multielectron oxidations forming stable radical cations, a property retained when incorporated in [2]rotaxanes, suggesting that pillar[5]arenes can be employed as viable, yet unreported, electron donors.

Isolating reactive metal-based species in Metal-Organic Frameworks - viable strategies and opportunities.

Structural insight into reactive species can be achieved strategies such as matrix isolation in frozen glasses, whereby species are kinetically trapped, or by confinement within the cavities of host molecules. More recently, Metal-Organic Frameworks (MOFs) have been used as molecular scaffolds to isolate reactive metal-based species within their ordered pore networks. These studies have uncovered new reactivity, allowed observation of novel metal-based complexes and clusters, and elucidated the nature of metal-centred reactions responsible for catalysis.

Influence of molecular design on radical spin multiplicity: characterisation of BODIPY dyad and triad radical anions.

A strategy to create organic molecules with high degrees of radical spin multiplicity is reported in which molecular design is correlated with the behaviour of radical anions in a series of BODIPY dyads. Upon reduction of each BODIPY moiety radical anions are formed which are shown to have different spin multiplicities by electron paramagnetic resonance (EPR) spectroscopy and distinct profiles in their cyclic voltammograms and UV-visible spectra. The relationship between structure and multiplicity is demonstrated showing that the balance between singlet, biradical or triplet states in the dyads depends on relative orientation and connectivity of the BODIPY groups.

Influence of Hydrogen-Bonding Interactions on Nuclearity and Structure of Palladium Tiara-like Complexes.

The role of intramolecular hydrogen-bonding interactions upon the nuclearity of palladium tiara-like complexes is reported herein. The synthesis of three palladium tiaras is described with three related thiolate ligands that vary in their hydrogen-bonding capability, amide vs ester for -acetylcysteamine (tiara ) vs 2-mercaptoethyl acetate (tiara ) or ethyl thioglycolate (tiara ), and in the relative position of the ester group, 2-mercaptoethyl acetate () or ethyl thioglycolate (). Mass spectrometry indicates that, in the absence of protic solvents, -acetylcysteamine reacts to form exclusively a six-membered tiara, [Pd(SCHCHNHCOCH)], , whereas the ester containing analogues form both six- and eight-membered tiaras.

Thionated Perylene Diimide-Phenothiazine Dyad: Synthesis, Structure, and Electrochemical Studies.

Perylene diimides (PDIs) are promising candidates for n-type semiconductor materials and, thus, for use in organic electronics. Thionation of the imide moiety provides an efficient strategy to control the donor-acceptor gap of these types of compounds, although the degree and selectivity of thionation can be hard to achieve. Through the design of a sterically encumbered PDI-phenothiazine dyad, a previously unattained geminal thionation pattern has been realized, providing the first example of a perylene-monoimide-monothioimide.