Beyond the Woodward-Hoffman rules: what controls reactivity in eliminative aromatic ring-forming reactions?

The Mallory (photocyclization) and Scholl (thermal cyclohydrogenation) reactions are widely used in the synthesis of extended conjugated systems of high scientific interest and technological importance, including molecular wires, semiconducting polymers and nanographenes. While simple electrocyclization reactions obey the Woodward-Hoffman rules, no such simple, general and powerful model is available for eliminative cyclization reactions due to their increased mechanistic complexity. In this work, detailed mechanistic investigations of prototypical reactions 10 reveal that there is no single rate-determining step for thermal oxidative dehydrogenation reactions, but they are very sensitive to the presence and distribution of heteroatoms around the photocyclizing ring system. Key aspects of reactivity are correlated to the constituent ring oxidation potentials. For photocyclization reactions, planarization occurs readily and/or spontaneously following photo-excitation, and is promoted by heteroatoms within 5-membered ring adjacent to the photocyclizing site. Oxidative photocyclization requires intersystem crossing to proceed to products, while reactants configured to undergo purely eliminative photocyclization could proceed to products entirely in the excited state. Overall, oxidative photocyclization seems to strike the optimal balance between synthetic convenience (ease of preparation of reactants, mild conditions, tolerant to chemical diversity in reactants) and favourable kinetic and thermodynamic properties

Role of host-guest interaction in understanding polymerisation in metal-organic frameworks

Metal-organic frameworks, MOFs, offer an effective template for polymerisation of polymers with precisely controlled structures within the sub-nanometre scales. However, synthetic difficulties such as monomer infiltration, detailed understanding of polymerisation mechanisms within the MOF nanochannels and the mechanism for removing the MOF template post polymerisation have prevented wide scale implementation of polymerisation in MOFs. This is partly due to the significant lack in understanding of the energetic and atomic-scale intermolecular interactions between the monomers and the MOFs. Consequently in this study, we explore the interaction of varied concentration of styrene, and 3,4-ethylenedioxythiophene (EDOT), at the surface and in the nanochannel of Zn2(1,4-ndc)2 (dabco), where 1,4-ndc = 1,4-naphthalenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. Our results showed that the interactions between monomers are stronger in the nanochannels than at the surfaces of the MOF. Moreover, the MOF-monomer interactions are strongest in the nanochannels and increase with the number of monomers. However, as the number of monomers increases, the monomers turn to bind more strongly at the surface leading to a potential agglomeration of the monomers at the surface

Predicting the outcome of photocyclisation reactions: a joint experimental and computational investigation

Photochemical oxidative cyclodehydrogenation reactions are a versatile class of aromatic ring-forming reactions. They are tolerant to functional group substitution and heteroatom inclusion, so can be used to form a diverse range of extended polyaromatic systems by fusing existing ring substituents. However, despite their undoubted synthetic utility, there are no existing models—computational or heuristic—that predict the outcome of photocyclisation reactions across all possible classes of reactants. This can be traced back to the fact that “negative” results are rarely published in the synthetic literature and the lack of a general conceptual framework for understanding how photoexcitation affects reactivity. In this work, we address both of these issues. We present experimental data for a series of aromatically substituted pyrroles and indoles, and show that quantifying induced atomic forces upon photoexcitation provides a powerful predictive model for determining whether a given reactant will photoplanarise and hence proceed to photocyclised product under appropriate reaction conditions. The propensity of a molecule to photoplanarise is related to localised changes in charge distribution around the putative forming ring upon photoexcitation. This is promoted by asymmetry in molecular structures and/or charge distributions, inclusion of heteroatoms and ethylene bridging and well-separated or isolated photocyclisation sites

Effect of unwanted guest molecules on the stacking configuration of covalent organic frameworks: a periodic energy decomposition analysis

Elucidating the precise stacking configuration of a covalent organic framework, COF, is critical to fully understand their various applications. Unfortunately, most COFs form powder crystals whose atomic characterisations are possible only through powder X-ray diffraction (PXRD) analysis. However, this analysis has to be coupled with computational simulations, wherein computed PXRD patterns for different stacking configurations are compared with experimental patterns to predict the precise stacking configuration. This task is often computationally challenging firstly because, computation of these systems mostly rely on the use of semi-empirical methods that need to be adequately parametrised for the system being studied and secondly because some of these compounds possess guest molecules, which are not often taken into account during computation. COF-1 is an extreme case in which the presence of the guest molecule plays a critical role in predicting the precise stacking configuration. Using this as a case study, we mapped out a full PES for the stacking configuration in the guest free and guest containing system using the GFN-xTB semi-empirical method followed by a periodic energy decomposition analysis using first-principles Density Functional Theory (DFT). Our results showed that the presence of the guest molecule leads to multiple low energy stacking configurations with significantly different lateral offsets. Also, the semi-empirical method does not precisely predict DFT low energy configurations, however, it accurately accounts for dispersion. Finally, our quantum-mechanical analysis demonstrates that electrostatic-dispersion model suggested Hunter and Sanders accurately describes the stacking in 2D COFs as opposed to the newly suggested Pauli-dispersion model

A dual-function highly crystalline covalent organic framework for HCl sensing and visible-light heterogeneous photocatalysis

Covalent organic frameworks (COFs) offer great potential for various advanced applications such as photocatalysis, sensing, and so on because of their fully conjugated, porous, and chemically stable unique structural architecture. In this work, we have designed and developed a truxene-based ultrastable COF (Tx-COF-2) by Schiff-base condensation between 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 5,5,10,10,15,15-hexamethyl-10,15-dihydro-5H-diindeno(1,2-a:1′,2′-c)fluorene-2,7,12-tricarbaldehyde (Tx-CHO) for the first time. The resulting COF possesses excellent crystallinity, permanent porosity, and high Brunauer–Emmett–Teller (BET) surface areas (up to 1137 m2 g–1). The COF was found to be a heterogeneous, recyclable photocatalyst for efficient conversion of arylboronic acids to phenols under visible-light irradiation, an environmentally friendly alternative approach to conventional metal-based photocatalysis. Besides, Tx-COF-2 provides an immediate naked-eye color change

Ionic covalent organic nanosheet (iCON)–quaternized polybenzimidazole nanocomposite anion-exchange membranes to enhance the performance of membrane capacitive deionization

Membrane capacitive deionization (MCDI) is a promising technique to achieve desalination of low-salinity water resources. The primary requirements for developing and designing materials for MCDI applications are large surface area, high wettability to water, high conductivity, and efficient ion-transport pathways. Herein, we synthesized ionic covalent organic nanosheets (iCONs) containing guanidinium units that carry a positive charge. A series of quaternized polybenzimidazole (QPBI)/iCON (iCON@QPBI) nanocomposite membranes was fabricated using solution casting. The surface, thermal, wettability, and electrochemical properties of the iCON@QPBI nanocomposite membranes were evaluated. The iCON@QPBI anion-exchange membranes achieved a salt adsorption capacity as high as 15.6 mg g−1 and charge efficiency of up to 90%, which are 50% and 20% higher than those of the pristine QPBI membrane, respectively. The performance improvement was attributed to the increased ion-exchange capacity (2.4 mmol g−1), reduced area resistance (5.4 Ω cm2), and enhanced hydrophilicity (water uptake = 32%) of the iCON@QPBI nanocomposite membranes. This was due to the additional quaternary ammonium groups and conductive ion transport networks donated by the iCON materials. The excellent desalination performance of the iCON@polymer nanocomposite membranes demonstrated their potential for use in MCDI applications and alternative electromembrane processes

Supramolecular chromatographic separation of C60 and C70 fullerenes: flash column chromatography vs. high pressure liquid chromatography

A silica-bound C-butylpyrogallol[4]arene chromatographic stationary phase was prepared and characterised by thermogravimetric analysis, scanning electron microscopy, NMR and mass spectrometry. The chromatographic performance was investigated by using C(60) and C(70) fullerenes in reverse phase mode via flash column and high-pressure liquid chromatography (HPLC). The resulting new stationary phase was observed to demonstrate size-selective molecular recognition as postulated from our in-silico studies. The silica-bound C-butylpyrogallol[4]arene flash and HPLC stationary phases were able to separate a C(60)- and C(70)-fullerene mixture more effectively than an RP-C(18) stationary phase. The presence of toluene in the mobile phase plays a significant role in achieving symmetrical peaks in flash column chromatography