Chemistry, Volume 3, Issue 1 (March 2021) – 32 articles

It is our great pleasure to introduce the Festschrift of Chemistry to honor professor Josef Michl (Figure 1) on the occasion of his 80th birthday and to recognize his exceptional contributions to the fields of organic photochemistry, quantum chemistry, biradicals and biradicaloids, electronic and vibrational spectroscopy, magnetic circular dichroism, silicon and boron chemistry, supramolecular chemistry, singlet fission, and molecular machines [...] Full article

We present a series of pyrazolato-bridged copper complexes with interesting structures that can be considered prototypic patterns for tri-, hexa- and hepta- nuclear systems. The trinuclear shows an almost regular triangle with a μ₃-OH central group. The hexanuclear has identical monomer units, the Cu₆ system forming a regular hexagon. The heptanuclear can be described as two trinuclear moieties sandwiching a central copper ion via carboxylate bridges. In the heptanuclear system, the pyrazolate bridges are consolidating the triangular faces, which are sketching an elongated trigonal antiprism. The magnetic properties of these systems, dominated by the strong antiferromagnetism along the pyrazolate bridges, were described transparently, outlining the energy levels formulas in terms of Heisenberg exchange parameters J, within the specific topologies. We succeeded in finding a simple Kambe-type resolution of the Heisenberg spin Hamiltonian for the rather complex case of the heptanuclear. In a similar manner, the weak intermolecular coupling of two trimer units (aside from the strong exchange inside triangles) was resolved by closed energy formulas. The hexanuclear can be legitimately proposed as a case of coordination-based aromaticity, since the phenomenology of the six-spins problem resembles the bonding in benzene. The Broken-Symmetry Density Functional Theory (BS-DFT) calculations are non-trivial results, being intrinsically difficult at high nuclearities. Full article

Of the utmost importance of chirality in organic compounds and drugs, the present work reports structure-chirality relationship of three steroidal quinoxalines, which were synthesised by condensing diaminobenzenes with cholestenone. All the compounds were purified and characterised by varying analytical tools prior to their chiroptical analysis by circular dichroism (CD) technique. The substituent groups on quinoxalines contributed to determining the chiroptical properties of the compounds. The positive Cotton effects have been observed in the CD spectra of unsubstituted and methyl-substituted quinoxalines, which indicated their P helicity. Importantly, chloro-substituent on quinoxalines produced different CD behaviour, which can be attributed to the presence of three lone pairs of electrons on Cl atom. The present work provides guidelines for determining the chiral properties of steroidal quinoxalines, which can be useful to design and develop potential molecules of biological importance. Full article

In this paper, we report the relationship between the anti-MERS-CoV activities of the HKU4 derived peptides for some peptidomimetic compounds and various descriptors using the quantitative structure activity relationships (QSAR) methods. The used descriptors were computed using ChemSketch, Marvin Sketch and ChemOffice software. The principal components analysis (PCA) and the multiple linear regression (MLR) methods were used to propose a model with reliable predictive capacity. The original data set of 41 peptidomimetic derivatives was randomly divided into training and test sets of 34 and 7 compounds, respectively. The predictive ability of the best MLR model was assessed by determination coefficient R² = 0.691, cross-validation parameter Q²_cv = 0.528 and the external validation parameter R²_test = 0.794. Full article

Nanometer-curved surfaces are abundant in biological systems as well as in nano-sized technologies. Properly functionalized polymer-grafted nanoparticles (PGNs) adhere to surfaces with different geometries and curvatures. This work explores some of the energetic and mechanical characteristics of the adhesion of PGNs to surfaces with positive, negative and zero curvatures using Coarse-Grained Molecular Dynamics (CGMD) simulations. Our calculated free energies of binding of the PGN to the curved and flat surfaces as a function of separation distance show that curvature of the surface critically impacts the adhesion strength. We find that the flat surface is the most adhesive, and the concave surface is the least adhesive surface. This somewhat counterintuitive finding suggests that while a bare nanoparticle is more likely to adhere to a positively curved surface than a flat surface, grafting polymer chains to the nanoparticle surface inverts this behavior. Moreover, we studied the rheological behavior of PGN upon separation from the flat and curved surfaces under external pulling force. The results presented herein can be exploited in drug delivery and self-assembly applications. Full article

In the present study, a quantitative structure–activity relationship (QSAR) and docking studies were accomplished on a series of 1,2,4-oxadiazoles. The results of QSARs are reliable and have high predictive ability for both the internal (q² = 0.610) and external (pred_r² = 0.553) datasets with least standard error (SE; i.e., 0.130) and four principal components, which signifies the reliability of the generated model. Molecular docking was also reported by the GOLD docking program, which showed that the hydrogen bonding may be responsible for the activity, and may be further increased upon adding high electronegative substitutions. Full article

Two analogous 2-D Hofmann-type frameworks, which incorporate the novel ligand N-(pyridin-4-yl)benzamide (benpy) [Fe^II(benpy)₂M(CN)₄]·2H₂O (M = Pd (Pd(benpy)) and Pt (Pt(benpy))) are reported. The benpy ligand was explored to facilitate spin-crossover (SCO) cooperativity via amide group hydrogen bonding. Structural analyses of the 2-D Hofmann frameworks revealed benpy-guest hydrogen bonding and benpy-benpy aromatic contacts. Both analogues exhibited single-step hysteretic spin-crossover (SCO) transitions, with the metal-cyanide linker (M = Pd or Pt) impacting the SCO spin-state transition temperature and hysteresis loop width (Pd(benpy): T_½↓↑: 201, 218 K, ∆T: 17 K and Pt(benpy): T_½↓↑: 206, 226 K, ∆T: 20 K). The parallel structural and SCO changes over the high-spin to low-spin transition were investigated using variable-temperature, single-crystal, and powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. These studies indicated that the ligand–guest interactions facilitated by the amide group acted to support the cooperative spin-state transitions displayed by these two Hofmann-type frameworks, providing further insight into cooperativity and structure–property relationships. Full article

We present an efficient strategy for synthesising the PdAu catalysts with a homogeneous PdAu alloy phase for environmentally important hydrodechlorination of tetrachloromethane in the gas phase. The synthesis of carbon-supported catalysts involved two major steps: (i) incorporation of palladium and gold nanoparticles into carbon support and (ii) activation of the catalysts. The critical part of this work was to find the optimal conditions for both steps. Thus, the incorporation of the nanoparticles was carried out in two ways, by impregnation and direct redox reaction method using acetone solutions of metal precursor salts. The activation was performed either by a conventional thermal reduction in hydrogen or flash irradiation in a microwave oven. The homogeneity and structure of the PdAu alloy were found to depend on the catalyst activation method critically. In all cases, we observed better homogeneity for catalysts that were subject to microwave irradiation. Moreover, the flash microwave irradiation of prepared catalysts provided catalysts of better stability and selectivity towards the desired products (hydrocarbons) in the hydrodechlorination of tetrachloromethane as compared to the catalyst obtained by conventional thermal activation in hydrogen. Full article

Carbon disulfide (CS₂) is a highly volatile neurotoxic species. It is known to cause atherosclerosis and coronary artery disease and contributes significantly to sulfur-based pollutants. Therefore, effective detection and capture of carbon disulfide represents an important aspect of research efforts for the protection of human and environmental health. In this study, we report the synthesis and characterization of two strongly luminescent and robust isoreticular metal organic frameworks (MOFs) Zr₆(µ₃-O)₄(OH)₈(tcbpe)₂(H₂O)₄ (here termed 1) and Zr₆(µ₃-O)₄(OH)₈(tcbpe-f)₂(H₂O)₄ (here termed 2) and their use as fluorescent sensors for the detection of carbon disulfide. Both MOFs demonstrate a calorimetric bathochromic shift in the optical bandgap and strong luminescence quenching upon exposure to carbon disulfide. The interactions between carbon disulfide and the frameworks are analyzed by in-situ infrared spectroscopy and computational modelling by density functional theory. These results reveal that both the Zr metal node and organic ligand act as the preferential binding sites and interact strongly with carbon disulfide. Full article

Polynuclear coordination clusters can be readily arranged in cluster-based coordination polymers (CCPs) by appropriate bridging linkers. This review provides an overview of our recent developments in exploring structurally well-defined Mn/Fe-oxo pivalate and isobutyrate building blocks in the formation of CCPs assemblies with an emphasis on synthetic strategies and magnetic properties. Full article

Few anions exhibit electronically excited states, and, if they do, the one or two possible excitations typically transpire beyond the visible spectrum into the near-infrared. These few, red-shifted electronic absorption features make anions tantalizing candidates as carriers of the diffuse interstellar bands (DIBs), a series of mostly unknown, astronomically ubiquitous absorption features documented for over a century. The recent interstellar detection of benzonitrile implies that cyano-functionalized polycyclic aromatic hydrocarbon (PAH) anions may be present in space. The presently reported quantum chemical work explores the electronic properties of deprotonated benzene, naphthalene, and anthracene anions functionalized with a single cyano group. Both the absorption and emission properties of the electronically excited states are explored. The findings show that the larger anions absorption and emission energies possess both valence and dipole bound excitations in the 450–900 nm range with oscillator strengths for both types of >$1\times {10}^{-4}$. The valence and dipole bound excited state transitions will produce slightly altered substructure from one another making them appear to originate with different molecules. The known interstellar presence of related molecules, the two differing natures of the excited states for each, and the wavelength range of peaks for these cyano-functionalized PAH anions are coincident with DIB properties. Finally, the methods utilized appear to be able to predict the presence of dipole-bound excited states to within a 1.0 meV window relative to the electron binding energy. Full article

Tetra Schiff bases were used as thermal stabilizers to enhance the properties of polyvinyl chloride (PVC) when operated at high temperatures. The thermal stability of PVC films doped with Schiff bases was tested by the weight-loss method, Fourier transform infrared (FTIR) spectroscopy, thermal aging test, optical microscope, and atomic force microscope (AFM). Results showed that embedding these additives increased the stability time of the polymer, which decreased the degradation reaction tendency. Furthermore, the primary color of PVC was improved by adding the Schiff bases using oven-aging. In addition, these Schiff bases resulted in a significant reduction in PVC’s conjugated double bonds and, hence, the weight loss. Full article

Three 2,1,3-benzothiadiazole-based ligands decorated with two pyridyl groups, 4,7-di(2-pyridyl)-2,1,3-benzothiadiazol (2-PyBTD), 4,7-di(3-pyridyl)-2,1,3-benzothiadiazol (3-PyBTD) and 4,7-di(4-pyridyl)-2,1,3 benzothiadiazol (4-PyBTD), generate Zn^II and Ag^I complexes with a rich structural variety: [Zn(hfac)₂(2-PyBTD)] 1, [Zn₂(hfac)₄(2-PyBTD)] 2, [Ag(CF₃SO₃)(2-PyBTD)]₂3, [Ag(2-PyBTD)]₂(SbF₆)₂4, [Ag₂(NO₃)₂(2-PyBTD)(CH₃CN)] 5, [Zn(hfac)₂(3-PyBTD)] 6, [Zn(hfac)₂(4-PyBTD)] 7, [ZnCl₂(4-PyBTD)₂] 8 and [ZnCl₂(4-PyBTD)] 9 (hfac = hexafluoroacetylacetonato). The nature of the resulting complexes (discrete species or coordination polymers) is influenced by the relative position of the pyridyl nitrogen atoms, the nature of the starting metal precursors, as well as by the synthetic conditions. Compounds 1 and 8 are mononuclear and 2, 3 and 4 are binuclear species. Compounds 6, 7 and 9 are 1D coordination polymers, while compound 5 is a 2D coordination polymer, the metal ions being bridged by 2-PyBTD and nitrato ligands. The solid-state architectures are sustained by intermolecular π–π stacking interactions established between the pyridyl group and the benzene ring from the benzothiadiazol moiety. Compounds 1, 2, 7–9 show luminescence in the visible range. Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT) calculations have been performed on the Zn^II complexes 1 and 2 in order to disclose the nature of the electronic transitions and to have an insight on the modulation of the photophysical properties upon complexation. Full article

The biomolecule chelidonic acid (H₂chel, 4-oxo-4H-pyran-2,6-dicarboxylic acid) has been used to build new coordination polymers with the bridging N,N′-ligands 4,4′-bipyridine (4,4-bipy) and 1,2-bis(4-pyridyl)ethane (bpe). Four compounds have been obtained as single crystals: 1D cationic coordination polymers [M(4,4-bipy)(OH₂)₄]²⁺ with chelidonate anions and water molecules in the second coordination sphere in ¹_∞[Zn(4,4-bipy)(H₂O)₄]chel·3H₂O (2) and in the two pseudopolymorphic ¹_∞[Cu(4,4-bipy)(H₂O)₄]chel·nH₂O (n = 3, 4a; n = 6, 4b), and the 2D neutral coordination polymers ²_∞[Zn(chel)(4,4-bipy)(H₂O)]·2H₂O (1) and ²_∞[Zn(chel)(bpe)(H₂O)]·H₂O (3) where the chelidonate anion acts as a bridging ligand. The effects of the hydrogen bonds on the crystal packing were analyzed. The role of the water molecules hosted within the crystals lattices was also studied. Full article

Carbon monoxide (CO) is an endogenously produced signaling molecule involved in the control of a vast array of physiological processes. One of the strategies to administer therapeutic amounts of CO is the precise spatial and temporal control over its release from photoactivatable CO-releasing molecules (photoCORMs). Here we present the synthesis and photophysical and photochemical properties of a small library of meso-carboxy BODIPY derivatives bearing different substituents at positions 2 and 6. We show that the nature of substituents has a major impact on both their photophysics and the efficiency of CO photorelease. CO was found to be efficiently released from π-extended 2,6-arylethynyl BODIPY derivatives possessing absorption spectra shifted to a more biologically desirable wavelength range. Selected photoCORMs were subjected to in vitro experiments that did not reveal any serious toxic effects, suggesting their potential for further biological research. Full article

The X-ray structure of racemic [Co(sep)][Co(edta)]Cl₂·2H₂O is reported and reveals hetero-chiral stereospecificity in the interactions of [Co(sep)]³⁺ with [Co(edta)]⁻. Hydrogen-bonding along the molecular C₂-axes of both complexes accounts for the stereospecificity. The structure of Λ-[Co(en)₃]∆-[Co(edta)]₂Cl·10H₂O has been re-determined. Previous structural data for this compound were collected at room temperature and the model did not sufficiently describe the disorder in the structure. The cryogenic temperature used in the present study allows the disorder to be conformationally locked and modeled more reliably. A clearer inspection of other, structurally interesting, interactions is possible. Again, hydrogen-bonding along the molecular C₂-axis of [Co(en)₃]³⁺ and the equatorial carboxylates of [Co(edta)]⁻ is the important interaction. The unique nature of the equatorial carboxylates and molecular C₂-axis in [Co(edta)]⁻, straddled by two pseudo-C₃-faces where the arrangement of the carboxylate groups conveys the same helicity, is highlighted. Implications of these structures in understanding stereoselectivity in ion-pairing and electron transfer reactions are discussed. Full article

Analysis of the weak interactions within the crystal structures of 33 complexes of various 4′-aromatic derivatives of 2,2′:6′,2″-terpyridine (tpy) shows that interactions that exceed dispersion are dominated, as expected, by cation⋯anion contacts but are associated with both ligand–ligand and ligand–solvent contacts, sometimes multicentred, in generally complicated arrays, probably largely determined by dispersion interactions between stacked aromatic units. With V(V) as the coordinating cation, there is evidence that the polarisation of the ligand results in an interaction exceeding dispersion at a carbon bound to nitrogen with oxygen or fluorine, an interaction unseen in the structures of M(II) (M = Fe, Co, Ni, Cu, Zn, Ru and Cd) complexes, except when 1,2,3-trimethoxyphenyl substituents are present in the 4′-tpy. Full article

We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu₂(μ-OAc)₄L]_n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu₂(μ-OAc)₄(1)]_n and [Cu₂(μ-OAc)₄(2)]_n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu₂(μ-OAc)₄(1)]_n and [Cu₂(μ-OAc)₄(2)]_n to [Cu₂(μ-OAc)₄(3)]_n, [Cu₂(μ-OAc)₄(4)]_n, and [Cu₂(μ-OAc)₄(5)]_n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility. Full article

Three-dimensional (3D) printing techniques have revolutionized the field of tissue engineering. This is especially favorable to construct intricate tissues such as liver, as 3D printing allows for the precise delivery of biomaterials, cells and bioactive molecules in complex geometries. Bioinks made of polymers, of both natural and synthetic origin, have been very beneficial to printing soft tissues such as liver. Using polymeric bioinks, 3D hepatic structures are printed with or without cells and biomolecules, and have been used for different tissue engineering applications. In this review, with the introduction to basic 3D printing techniques, we discuss different natural and synthetic polymers including decellularized matrices that have been employed for the 3D bioprinting of hepatic structures. Finally, we focus on recent advances in polymeric bioinks for 3D hepatic printing and their applications. The studies indicate that much work has been devoted to improvising the design, stability and longevity of the printed structures. Others focus on the printing of tissue engineered hepatic structures for applications in drug screening, regenerative medicine and disease models. More attention must now be diverted to developing personalized structures and stem cell differentiation to hepatic lineage. Full article

N,N′,N″,N‴-Tetraisopropylpyrophosphoramide 1 is a pyrophosphoramide with documented butyrylcholinesterase inhibition, a property shared with the more widely studied octamethylphosphoramide (Schradan). Unlike Schradan, 1 is a solid at room temperature making it one of a few known pyrophosphoramide solids. The crystal structure of 1 was determined by single-crystal X-ray diffraction and compared with that of other previously described solid pyrophosphoramides. The pyrophosphoramide discussed in this study was synthesised by reacting iso-propyl amine with pyrophosphoryl tetrachloride under anhydrous conditions. A unique supramolecular motif was observed when compared with previously published pyrophosphoramide structures having two different intermolecular hydrogen bonding synthons. Furthermore, the potential of a wider variety of supramolecular structures in which similar pyrophosphoramides can crystallise was recognised. Proton (¹H) and Phosphorus 31 (³¹P) Nuclear Magnetic Resonance (NMR) spectroscopy, infrared (IR) spectroscopy, mass spectrometry (MS) were carried out to complete the analysis of the compound. Full article

Lanthanide (Ln^III) ions were successfully chelated and sensitized with a tripodal ligand. The absolute Ln^III-centered emission efficiencies were ~3% for both the europium(III) (Eu^III) and terbium (Tb^III) complexes and up to 54% for the cerium(III) (Ce^III) complex. The differences in emission quantum yields for the early lanthanides (Ce^III) and the mid lanthanides (Eu^III and Tb^III) were attributed to their d–f and f–f nature, respectively. Despite the low quantum yield of the Eu^III complex, the combination of the residual ligand fluorescence and the red Eu^III emission resulted in a bluish-white material with the Commission Internationale de l’Eclairage (CIE) coordinates (0.258, 0.242). Thus, metal complexes of the ligand could be used in the generation of single-component white-light-emitting materials. Full article

We present a holistic crystallographic study of the antiviral ganciclovir, including insights into its solid-state behavior, which could prove useful during drug development, making the process more sustainable. A newly developed methodology was used incorporating a combination of statistical and thermodynamic approaches, which can be applied to various crystalline materials. We demonstrate how the chemical environment and orientation of a functional group can affect its accessibility for participation in hydrogen bonding. The difference in the nature and strength of intermolecular contacts between the two anhydrous forms, exposed through full interaction maps and Hirshfeld surfaces, leads to the manifestation of conformational polymorphism. Variations in the intramolecular geometry and intermolecular interactions of both forms of ganciclovir were identified as possible predictors for their relative thermodynamic stability. It was shown through energy frameworks how the extensive supramolecular network of contacts in form I causes a higher level of compactness and lower enthalpy relative to form II. The likelihood of the material to exhibit polymorphism was assessed through a hydrogen bond propensity model, which predicted a high probability associated with the formation of other relatively stable forms. However, this model failed to classify the stability of form I appropriately, suggesting that it might not have fully captured the collective impacts which govern polymorphic stability. Full article

Three distinct four-component supramolecular nanorotors were prepared, using, for the first time, bipyridine instead of phenanthroline stations in the stator. Following our established self-sorting protocol to multicomponent nanodevices, the nanorotors were self-assembled by mixing the stator, rotators with various pyridine head groups, copper(I) ions and 1,4-diazabicyclo[2.2.2]octane (DABCO). Whereas the exchange of a phenanthroline vs. a bipyridine station did not entail significant changes in the rotational exchange frequency, the para-substituents at the pyridine head group of the rotator had drastic consequences on the speed: 4-OMe (k₂₉₈ = 35 kHz), 4-H (k₂₉₈ = 77 kHz) and 4-NO₂ (k₂₉₈ = 843 kHz). The exchange frequency (log k) showed an excellent linear correlation with both the Hammett substituent constants and log K of the copper(I)–ligand interaction, proving that rotator–copper(I) bond cleavage is the key determining factor in the rate-determining step. Full article

A series of free base meso-tetraarylporphyrins functionalized with substituents containing one, two, and four cyclooctatetraene (COT) moieties have been obtained and characterized by spectral and photophysical studies. Three COT-free porphyrins served as reference compounds. COT is a triplet quencher, well-known to enhance the photostability of several, but not all, fluorophores. In the case of porphyrins, substitution with COT improves photostability in zinc derivatives, but for free bases, the effect is the opposite. We show that placing the COT moiety further from the free base porphyrin core enhances the photostability when the COT group lies in the direct vicinity of the macrocycle. The quantum yields of photobleaching inversely correlate with porphyrin oxidation potentials. An improvement in photostability in both COT-containing and COT-free porphyrins can be achieved by screening the porphyrin core from oxygen by switching from tolyl to mesityl substituents. This leads to a decrease in the photobleaching quantum yield, even though triplet lifetimes are longer. The results confirm the involvement of oxygen in the photodegradation of porphyrins. Full article

Theoretical DFT calculations using GGA+U and HSE06 frameworks enabled vibrational mode assignment and partial (atomic) phonon DOS determination in KAgF₃ perovskite, a low-dimensional magnetic fluoroargentate(II). Twelve bands in the spectra of KAgF₃ were assigned to either IR active or Raman active modes, reaching excellent correlation with experimental values (R2 > 0.997). Low-temperature Raman measurements indicate that the intriguing spin-Peierls-like phase transition at 230 K is an order–disorder transition and it does not strongly impact the vibrational structure of the material. Full article

The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD), with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity, have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G (d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol⁻¹ in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study establishes the depopulation of the N–N–C core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration. Full article

During a systematic study of monofluorophosphates, i.e., compounds comprising the tetrahedral anion PO₃F²⁻, twelve, for the most part new, compounds were obtained from aqueous solutions. Crystal structure refinements based on single crystal X-ray diffraction data revealed the previously unknown crystal structures of CdPO₃F(H₂O)₂, Cr₂(PO₃F)₃(H₂O)_18.8, Pb₂(PO₃F)Cl₂(H₂O), (NH₄)₂M(PO₃F)₂(H₂O)₂ (M = Mg, Mn, Co), NH₄Cr(PO₃F)₂(H₂O)₆, NH₄Cu₂(H₃O₂)(PO₃F)₂, (NH₄)₂Zn(PO₃F)₂(H₂O)_0.2, and (NH₄)₂Zn₃(PO₃F)₄(H₂O), as well as redeterminations of ZnPO₃F(H₂O)_2.5 and (NH₄)₂Ni(PO₃F)₂(H₂O)₆. From the previously unknown crystal structures, CdPO₃F(H₂O)₂ (space group P$\overline{1}$), Cr₂(PO₃F)₃(H₂O)_18.8 (P$\overline{1}$), Pb₂(PO₃F)Cl₂(H₂O) (Pnma), NH₄Cr(PO₃F)₂(H₂O)₆ (R$\overline{3}$m), (NH₄)₂Zn(PO₃F)₂(H₂O)_0.2 (C2/c), and (NH₄)₂Zn₃(PO₃F)₄(H₂O) (I$\overline{4}$3d) each crystallizes in an unique crystal structure, whereas compounds (NH₄)₂M(PO₃F)₂(H₂O)₂ (M = Mg, Co) crystallize in the (NH₄)₂Cu(PO₃F)₂(H₂O)₂ type of structure (C2/m) and (NH₄)₂Mn(PO₃F)₂(H₂O)₂ in a subgroup thereof (P2₁/n, with a klassengleiche relationship of index 2), and NH₄Cu₂(H₃O₂)(PO₃F)₂ (C2/m) crystallizes isotypically with natrochalcite-type KCu₂(H₃O₂)(SO₄)₂. A survey on the PO₃F²⁻ anion, including database entries of all inorganic compounds comprising this group, revealed mean bond lengths of P–O = 1.506(13) Å, P–F = 1.578(20) Å, and angles of O–P–O = 113.7(1.7)° and O–P–F = 104.8(1.7)°, using a dataset of 88 independent PO₃F²⁻ anions or entities. For those crystal structures of monofluorophosphates where hydrogen bonding is present, in the vast majority of cases, hydrogen bonds of the type D–H···F–P (D = O, N) are not developed. Full article

Molecular rotors have earned substantial popularity in recent times, owing to the unique dependence of its crystalline properties on the rotational dynamics of the rotor. We have recently reported the synthesis and crystal structure of a phenylene-bridged macrocage as a gyroscope-like molecule in the crystalline state. The dynamics of the phenylene moiety was probed by solid-state ¹³C CP/MAS proton dipolar dephasing NMR spectroscopy. Herein, solid-state ²H NMR studies were performed to study the dynamics of the gyroscope-like molecule with a deuterated rotor in the crystalline state. A spectrum with a narrow line shape was obtained at 300 K. The facile exchange among three stationary states, which was observed by X-ray crystallography, was clearly confirmed. Additionally, a crystal-to-crystal phase transition that switches the motion of the rotor was observed in the DSC analysis of the powdered sample. Full article

By following the intrinsic reaction coordinate connecting transition states with energy minima on the potential energy surface, we have determined the reaction steps connecting three-dimensional hexaborane(12) with unknown planar two-dimensional hexaborane(12). In an effort to predict the potential synthesis of finite planar borane molecules, we found that the reaction limiting factor stems from the breaking of the central boron-boron bond perpendicular to the C₂ axis of rotation in three-dimensional hexaborane(12). Full article