ChemPlusChem最新文献

The front cover shows photoinduced electron and energy transfer pathways in all perylene diimide-derived, wide-band capturing donor-acceptor conjugates as a mimicry of the early events of natural photosynthesis. Selective excitation of the charge transfer band in these conjugates leads to an initial singlet charge transfer excited state that undergoes subsequent electron transfer involving linked perylene diimide, resulting in efficient charge separation. More details can be found in the Research Article by Fernando Fernández-Lázaro, Francis D'Souza, and co-workers (DOI: 10.1002/cplu.202400348).

The cover feature shows amino-functionalized (blue gloves) assisting enhanced CO₂ uptake compared to unfunctionalized (white gloves) MOFs. The amino-functionalized MOF holds 3 CO₂ molecules while the unfunctionalized MOF holds only 2 CO₂ molecules, according to the ratio of adsorption capacities at 273 K at 1 bar. The recorded gas adsorption isotherms at 273 K are shown in the background highlighting the affinity of MOFs for CO₂ over N₂. More details can be found in the Research Article by Sachin Maruti Chavan and co-workers (DOI: 10.1002/cplu.202400107).

Acetylene is in-demand even on Titan! The cover picture shows Titan - the moon of Saturn. Titan is unique in having an atmosphere and hydrocarbons. Acetylene was discovered on Titan, but its amount constantly decreases over time, which may indicate its consumption by living organisms. On Earth, acetylene is a ton-scale product of the chemical industry. Methods for manufacturing acetylene and the cost of each method can be found in the Review by Konstantin Rodygin and co-workers (DOI: cplu.202400247). Cover design by Andrei Lebedev.

The sustainable synthesis of urea from ammonia (NH₃) and carbon dioxide (CO₂) using ultraporous permanently polarized hydroxyapatite (upp-HAp) as catalyst has been explored as an advantageous CO₂-revalorization strategy. As the simultaneous activation of N₂ and CO₂ (single-step) demands an increase of the reaction conditions, we have re-visited the industrial two-step Bazarov reaction. upp-HAp has been designed as a stable multifunctional catalyst capable of promoting both CO₂ and NH₃ adsorption for their subsequent C−N bond formation. Herein we report the synthesis of 1 mmol/g_cat of urea with a selectivity of 97 % under strictly mild conditions (95–120 °C and 1 bar of CO₂; without applying any electrical currents or UV irradiation) which represents an efficiency of ~2 % and ~30 % with respect to the NH₃ and CO₂ content, respectively. The study of the NH₃ content, products adsorbed in the catalyst, presence of intermediates and temperature of the reaction allows unveiling the great potential of upp-HAp as a green catalyst for sustainable Bazarov reactions. Results suggest that the double-step approach could be more advantageous for both synthesizing urea and as a CO₂-revalorization strategy, which in turn promotes the development of specific technologies for the independent synthesis of green NH₃.

New chemical compositions and structures for medium- and high-entropy oxides (HEOs) currently represent a promising new avenue in materials research for a wide range of applications including catalysis, energy storage, and ceramics. To speed up further development, synthesis methods for multicationic oxides are needed for controlling features like morphology, porosity, and chemical compositions. In this work, mesoporous spinel oxide spheres with five cations are synthesized using solvothermal synthesis techniques. The targeted chemistry included Co, Al, Fe, and Cr as the first four cations, where the fifth cation was varied by increasing cation radii (Ga, In, Yb, Ho, or Ce). After calcination, all as-synthesized precursors led to mesoporous oxide spheres with spinel oxide structures. In order to demonstrate an example of applicability for targeting different M³⁺ cations, the sample containing Co, Al, Fe, Cr, and In was tested in a model reaction of thermocatalytic CO₂ hydrogenation and is shown to be active with a preference to methanol formation (58 % selectivity, 7.8 % conversion at 300 °C). The synthesis of multicationic mesoporous spheres appears to be quite flexible in terms of possible M³⁺ cations compositions and is a potential material to combine targeted chemistry for applications like catalysis.

The research and development of push-pull tetraene chromophores (PPT-phores) have contributed greatly to the field of organic electro-optic (EO) materials and devices since the inauguration of CLD-1 in 2001. This study is thus a systematic contribution to synthesize and characterize a series of centro-arylated PPT-phores based on strong electron-donating tetrahydroquinolinyl groups and variable strong electron-accepting tricyanofuran derivatives. In particular, we report the crystallographic data to show various packing modes of these PPT-phores with detailed information about bond length alternation and intermolecular interactions, the optical absorption edges of guest-host polymers by the Tauc model, and the anisotropy and dispersion of Pockels tensors for the poled polymers by attenuated total reflection spectroscopy. Such analyses have not been addressed to any significant extent previously and are fundamentally important to the future development of PPT-phore-based EO materials and devices. The poled films of several centro-arylated PPT-phores in polycarbonates exhibited large EO activities, excellent thermal stability, and tunable optical transparency at the telecom O- and C-band. The study demonstrates the effectiveness of π-bridge centro-arylation enabled by molecular shape modification and rigidity enhancement, over the relatively flexible and labile thioether or alkoxy groups, in rational design of hyperpolarizable PPT-phores for high-performance EO polymers.

Metal ion detection is of paramount importance for health monitoring. The host should properly accommodate the desired ion and be selective with respect to other potential guests, which makes devising ion sensors a demanding task. Recently (Phys. Chem. Chem. Phys. 2023, 25, 32656), we suggested a procedure for a computational design of crown ethers that can capture magnesium ions. In the present contribution we apply the same approach to search for Mg²⁺ trap with thiophene units, in accord with proposed hosts for Na⁺ and K⁺ ions (Adv. Funct. Mater. 2016, 26, 514). Additionally, we present a procedure based on the combination of Density Functional Theory based Molecular Dynamics and the Interacting Quantum Fragments methodology for determination of host–guest interaction and binding energies in a model with a large number of explicit solvent molecules. The presented strategy could be applied for identification of the right host for an arbitrary guest.

The invention of laminated safety glass is attributed to the French chemist and artist Edouard Benedictus (1878–1930), who developed the innovation known as Triplex glass after inspiration struck via a fortuitous laboratory accident. Licensed first to the English Triplex Safety Glass Company in 1912, with production later carried out in the US, Triplex glass was first applied to automobiles during the first World War. While the story of his lab accident can be found in many sources, it has become more legend than historical fact. To rectify this, a more accurate account of Benedictus and the development of Triplex glass is presented based on historical records.

Vibrational spectroscopy can be said to have started with the seminal work of Coblentz in the 1900s, who recorded the first recognisable infrared spectra. Today, vibrational spectroscopy is ubiquitous and there are many ways to measure a vibrational spectrum. But this is usually only the first step, almost always there is a need to assign the resulting spectra: “what property of the system results in a feature at this energy”? How this question has been answered has changed over the last century, as our understanding of the fundamental physics of matter has evolved. In this Perspective, I will present my view of how the analysis of vibrational spectra has evolved over time. The article is divided into three sections: past, present and future. The “past” section consists of a very brief history of vibrational spectroscopy. The “present” is centered around ab initio studies, particularly with density functional theory (DFT) and I will describe how this has become almost routine. For the “future”, I will extrapolate current trends and also speculate as to what might come next.

Nanoparticles of metal-organic frameworks (nanoMOFs) possess the unusual combination of both internal and external surfaces. While internal surfaces have been the focus of fundamental and applications-based MOF studies, the chemistry of the external surfaces remains scarcely understood. Herein we report that specific ion interactions with nanoparticles of Cu(1,2,3-triazolate)₂ (Cu(TA)₂) resemble the Hofmeister behavior of proteins and the supramolecular chemistry of synthetic macromolecules. Inspired by these anion-selective interactions, we tested the performance of Cu(TA)₂ nanoparticles as chemical field effect transistor (ChemFET) anion sensors. Rather than size-based selectivity, the detection limits of the devices exhibit a Hofmeister trend, with the greatest sensitivity towards anions perchlorate, iodide, and nitrate. These results highlight the importance of the pore-based supramolecular interactions, rather than localized donor-acceptor pairs, in designing MOF-based technologies.