Correction: Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine.

Correction for 'Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine' by Kacper Poblocki et al., Dalton Trans., 2024, 53, 4194-4203, https://doi.org/10.1039/D3DT04091G.

Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine.

There are few literature reports on using precatalysts based on ruthenium(II/III) ions in the polymerization of olefins. Therefore, a new coordination compound was designed based on ruthenium(III) ion and 2-phenylpyridine. The resulting monocrystal was characterized by X-ray diffraction (XRD), solid-state (photo)IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The new ruthenium(III) complex compound was used as a precatalyst in the oligomerization reactions of ethylene, 2-propen-1-ol, 2-chloro-2-propen-1-ol, 3-butene-2-ol and 2,3-dibromo-2-propen-1-ol with methylaluminoxane and ethylaluminium dichloride as activators. The catalytic activity of the newly discovered ruthenium(III) complex compound ranges from 159.5 (for 2-chloro-2-propen-1-ol) to 755.6 (for ethylene) g mmol-1 h-1 bar-1, indicating that it is a chemical compound with high catalytic activity. In addition, the oligomerization reaction products were subjected to physicochemical characterization, using BET (Brunauer-Emmett-Teller isotherm), mass spectrometry (MALDI-TOF-MS), Fourier transform infrared (FT-IR) spectroscopy, NMR, TGA, differential scanning calorimetry (DSC), and the morphology of the porous polymeric materials was investigated by SEM. The distinguishing feature of the obtained precatalyst is its high catalytic activity under mild reaction conditions, a rare phenomenon. Compared with other precatalysts, it is the most active ruthenium(II/III) ion-based catalytic material used in oligo- and polymerization reactions of ethylene.

Interrelations between Linkage Isomers of an Efficient Square-planar Nickel(II) Nitrite Photoswitch in the Solid State.

An efficient nitrite nickel(II) photoswitch, with the 1-phenyl-2-hydroxyimino-3-[(2'-dimethylamino)ethyl]imino-1-propanone moiety used as the ancillary ligand, is reported. In the ground-state ('dark') crystal structure, the studied compound exists predominantly as the nitro-(η1 -N(O)2 ) isomer, however, traces of the exo- and endo-nitrito-(η1 -ONO) forms are detected both at 100 K (4-5 % each) and under ambient conditions (~9 % each). When excited with the 405-530 nm LED light, the nitro-to-nitrito isomerization takes place. The total conversion exceeds 90 %. The exo-nitrito linkage isomer constitutes the dominant photo-generated form, whereas the relative population of both nitrito species depends on temperature. The reaction is fully reversible and reproducible. The photo-products are stable up to 200 K. The system constitutes a good model case for the reaction mechanism studies. Thus, experimental and theoretical investigations on the photo-isomerism were conducted and are presented in detail. Eventually, the nitro→exo-nitrito→endo-nitrito reaction pathway is proposed.

Catalytic Properties of Two Complexes of chromium(III) and cobalt(II) with Nitrilotriacetate, Dipicolinate, and 4-Acetylpyridine.

In this paper, a synthesis of two innovative coordination compounds, based on chromium(III) and cobalt(II) ions with N,O-donor ligands (nitrilotriacetate, dipicolinate) and 4-acetylpyridine, is reported. The obtained metal-organic compounds were structurally characterized using the single-crystal X-ray diffraction (XRD) method. The well-defined chromium(III) and cobalt(II) complexes were used as precatalysts in the oligomerization reaction of 2-chloro-2-propen-1-ol and 2-propen-1-ol with methylaluminoxane (MMAO) as an activator. The products of the oligomerization reaction were subjected to full physicochemical characteristics, i.e., time-of-flight mass spectrometry (MALDI-TOF-MS), TGA, and differential scanning calorimetry (DSC) methods. The catalytic activity of the precatalysts in both reactions was calculated and compared with other catalysts known in the literature.

Correction: An optically reversible room-temperature solid-state cobalt(III) photoswitch based on nitro-to-nitrito linkage isomerism.

Correction for 'An optically reversible room-temperature solid-state cobalt(III) photoswitch based on nitro-to-nitrito linkage isomerism' by Krystyna A. Deresz et al., Chem. Commun., 2022, 58, 13439-13442, https://doi.org/10.1039/d2cc05134f.

An optically reversible room-temperature solid-state cobalt(III) photoswitch based on nitro-to-nitrito linkage isomerism.

A simple trinitro cobalt complex [Co(3,3'-diamino-N-methylpropanediamine)(NO2)3] was proven to be photoswitchable at room temperature as the Pca21 polymorph with the maximum nitro-to-nitrito conversion reaching ca. 55%. Solid-state IR, UV-vis and XRD indicate that the transformation can be triggered optically in both ways via 470 nm and 570-660 nm LED light, respectively.

Exploring Photoswitchable Properties of Two Nitro Nickel(II) Complexes with (N,N,O)-Donor Ligands and Their Copper(II) Analogues.

Two photoswitchable nickel(II) nitro coordination compounds and their copper(II) analogues are reported. In all these systems, the metal center is chelated by (N,N,O)-donor ligands containing either 2-picolylamine or 8-aminoquinoline fragments. The studied compounds were thoroughly investigated using crystallographic and spectroscopic techniques supplemented by computational analysis. They are easy to synthesize and stable, and all compounds undergo the nitro group isomerization reaction. Nevertheless, there are significant differences between the copper and nickel systems regarding their structural and switchable properties. According to the solid-state IR spectroscopy results, 400-660 nm light irradiation of the ground-state (η2-O,O')-κ-nitrito copper(II) complexes at 10 K induces a rather moderate conversion to a metastable linkage isomer, which is visible only up to approximately 60-80 K. In turn, upon visible light irradiation (ca. 530 nm excitation wavelength), the ground-state nitro isomers of the examined nickel(II) complexes transform into the endo-nitrito forms. It was possible to achieve about 35% conversion for both nickel(II) systems and to determine the resulting crystal structures at 160 K in the case of single crystals after 30-45 min of exposure to LED light (crystals decayed with longer irradiation), and roughly 95% conversion was achieved for thin-film samples as indicated by the IR spectroscopy results. Traces of the endo-nitrito linkage isomers remained up to 200-220 K, and the isomerization reaction was proven to be fully reversible.

Expedient Synthesis of Oxaboracyclic Compounds Based on Naphthalene and Biphenyl Backbone and Phase-Dependent Luminescence of their Chelate Complexes.

The approach to a series of six- and seven-membered oxaboraheterocycles based on naphthalene or biphenyl backbones was developed. The key synthetic step involved Br/Li exchange in respective potassium (bromoaryl)trifluoroborates followed by quenching with selected electrophiles (CO2 , DMF, Me2 Si(H)Cl) and hydrolytic workup. Two ring-expanded benzoxaborole congeners were obtained by an additional reduction step with LiAlH4 or NaBH4 . The obtained boracyclic compounds were characterized in detail by NMR spectroscopy and single-crystal X-ray diffraction. Specifically, biphenyl-based systems show dynamic behaviour interpreted in terms of inversion of non-planar seven-membered boraheterocycles. The acidity of the obtained compounds varies very strongly (pKa ranges from 3.1-9.6) depending on their structure. Due to the enhanced boron Lewis acidity, selected compounds were used as a basis for luminescent complexes with 8-hydroxyquinoline. A strong phase-dependent variation of emission-band maximum (480-527 nm) and photoluminescence quantum yield (10-95 %) was observed, which was rationalized in terms of specific aggregation effects.

9,10-Anthraquinones Disubstituted with Linear Alkoxy Groups: Spectroscopy, Electrochemistry, and Peculiarities of Their 2D and 3D Supramolecular Organizations.

Spectroscopic, electrochemical, and structural properties of 2,6-dialkoxy-9,10-anthraquinones (Anth-OCn, n = 4, 6, 8, 10, and 12) of increasing alkoxy substituents length were investigated. UV-vis spectroscopy showed a substitution-induced bathochromic shift of the least energetic band from 325 nm in the case of unsubstituted anthraquinone to ca. 350 nm for the studied derivatives. Similarly as unsubstituted anthraquinone, the studied compound showed two reversible one electron reductions to a radical anion and spinless anions, respectively. The first reduction was affected by electron-donating properties of the substituents, its potential being shifted to ca. -1.5 V (vs Fc/Fc+), i.e., by 80 to 95 mV as compared to the case of unsubstituted anthraquinone. This corresponded to a decrease of |EA| from 3.27 to 3.19-3.17 eV. The experimental spectroscopic and electrochemical data were in full agreement with the DFT calculations. The introduction of the alkoxy substituent improved solution processibility of the studied compounds and facilitated the formation of their ordered supramolecular 2D aggregation on HOPG as well as single crystal growth from solutions. Comparative structural investigations carried out on single crystals and monolayers deposited on HOPG revealed two, mutually related, effects of the substituent length on the resulting supramolecular organization. The first one concerns both the 2D organization in the monolayers and 3D molecular arrangement in crystals: increasing substituent length evolution of the structure occurs from herringbone-type to lamellar. The second effect, observed in monolayers of the derivatives with longer substituents, concerns gradual evolution of their lamellar structures with increasing substituent length. This evolution is induced by the structure of the graphite substrate and involves increasing correlation of the molecules orientation (anthraquinone cores as well as alkoxy substituents) with the symmetry of the graphite substrate. As a result, their 2D and 3D structures become dissimilar.

Photocrystallographic and spectroscopic studies of a model (N,N,O)-donor square-planar nickel(II) nitro complex: in search of high-conversion and stable photoswitchable materials.

A new, cheap, easy-to-synthesize and air-stable photoswitchable nickel(II) complex, QTNiNO2, is reported. The metal centre in QTNiNO2 is coordinated by a nitro group and a [2-methyl-8-amino-quinoline]-1-tetralone ligand. The compound crystallizes in the tetragonal space group I41/a with one complex molecule comprising the asymmetric unit, and the crystals are stable under ambient conditions. Irradiation of the solid-state form of QTNiNO2 with 530-660 nm LED light at 160 K converts the ambidentate nitro moiety fully to the nitrito linkage isomer which is stable up to around 230 K, as indicated by IR spectroscopy measurements. The structures of all species present in the examined crystals and their thermal stability were confirmed via X-ray multi-temperature and photocrystallographic experiments. The impact of temperature on the (photo)isomerization reaction taking place in a single crystal was additionally investigated. The experimental results are supported by computational analyses of crystal packing and intermolecular interactions that influence the isomerization process studied.

Instrument-model refinement in normalized reciprocal-vector space for X-ray Laue diffraction.

A simple yet efficient instrument-model refinement method for X-ray diffraction data is presented and discussed. The method is based on least-squares minimization of differences between respective normalized (i.e. unit length) reciprocal vectors computed for adjacent frames. The approach was primarily designed to work with synchrotron X-ray Laue diffraction data collected for small-molecule single-crystal samples. The method has been shown to work well on both simulated and experimental data. Tests performed on simulated data sets for small-molecule and protein crystals confirmed the validity of the proposed instrument-model refinement approach. Finally, examination of data sets collected at both BioCARS 14-ID-B (Advanced Photon Source) and ID09 (European Synchrotron Radiation Facility) beamlines indicated that the approach is capable of retrieving goniometer parameters (e.g. detector distance or primary X-ray beam centre) reliably, even when their initial estimates are rather inaccurate.

Seed-skewness algorithm for X-ray diffraction signal detection in time-resolved synchrotron Laue photocrystallography.

A one-dimensional seed-skewness algorithm adapted for X-ray diffraction signal detection is presented and discussed. The method, primarily designed for photocrystallographic time-resolved Laue data processing, was shown to work well for the type of data collected at the Advanced Photon Source and European Synchrotron Radiation Facility. Nevertheless, it is also applicable in the case of standard single-crystal X-ray diffraction data. The reported algorithm enables reasonable separation of signal from the background in single one-dimensional data vectors as well as the capability to determine small changes of reflection shapes and intensities resulting from exposure of the sample to laser light. Otherwise, the procedure is objective, and relies only on skewness computation and its subsequent minimization. The new algorithm was proved to yield comparable results to the Kruskal-Wallis test method [Kalinowski, J. A. et al. (2012). J. Synchrotron Rad. 19, 637], while the processing takes a similar amount of time. Importantly, in contrast to the Kruskal-Wallis test, the reported seed-skewness approach does not need redundant input data, which allows for faster data collections and wider applications. Furthermore, as far as the structure refinement is concerned, the reported algorithm leads to the excited-state geometry closest to the one modelled using the quantum-mechanics/molecular-mechanics approach reported previously [Jarzembska, K. N. et al. (2014). Inorg. Chem. 53, 10594], when the t and s algorithm parameters are set to the recommended values of 0.2 and 3.0, respectively.

Photo- and Thermoswitchable Half-Sandwich Nickel(II) Complex: [Ni(η5-C5H5)(IMes)(η1-NO2)].

A new photoswitchable half-sandwich nitro NiII complex with the N-heterocyclic carbene ligand was synthesized and successfully crystallized. The compound constitutes an analogue of a known nitrate nickel(II) compound, [Ni(η5-Cp)(IMes)(NO3)] (Cp = cyclopentadienyl, C5H5; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and crystallizes with two symmetry-independent molecules in the asymmetric unit. When irradiated with 470 nm light-emitting diode light, the complex molecules undergo a photoisomerization reaction in the solid state. Formation of the respective NO2 group linkage isomers was studied photocrystallographically at different temperatures. After irradiation of the single-crystal sample for ca. 3 h at 100 K approximately 20% conversion of the η1-nitro (Ni-NO2) ligand to its exo-nitrito (Ni-ONO) form was observed. At ∼130 K the exo-nitrito binding mode transforms further to the more stable endo-nitrito conformation, whereas at temperatures higher than 175 K the crystal converts back to the ground state. It appears that the photoisomerization reaction can be to some extent triggered, or additionally stimulated, thermally. Consequently, the highest conversion level (ca. 90%) was achieved after sample irradiation at 145 K. Despite similar molecular energies and intermolecular interactions, the two symmetry-independent molecules behave somewhat differently upon irradiation and temperature changes. The photocrystallographic findings and molecular aspects were supplemented by theoretical computations, including the quantum-mechanics/molecular-mechanics approach.

Impact of High Pressure on Metallophilic Interactions and Its Consequences for Spectroscopic Properties of a Model Tetranuclear Silver(I)-Copper(I) Complex in the Solid State.

Structure-property relationships were investigated via combined high-pressure spectroscopic and X-ray diffraction techniques for a model luminescent Ag2Cu2L4 (L = 2-diphenylphosphino-3-methylindole) complex in the crystalline state. The experimental results were contributed by theoretical calculations, compared with the previously evaluated light-induced geometrical changes, and discussed in the context of available literature to date. To the best of our knowledge, this is the first study of this kind devoted to a coinage-metal complex for which the argentophilic interactions are crucial. High-pressure X-ray diffraction and optical spectroscopy experiments showed close correspondence between structural changes and optical properties. The unit-cell angles, absorption edges, emission maxima, decay lifetimes and silver-copper bond trends, all change around 2-3 GPa. A blue-shift to red-shift switch when increasing the pressure was observed for both absorption and emission spectra. This is unique behavior when compared to the literature-reported coinage metal systems. It also occurred that the pressure-induced structural changes differ notably from the geometrical distortions observed for the excited state. Interestingly, shortening of the Ag-Ag bond itself does not ensure the red shift of the absorption and emission spectra. All the optical spectroscopy data are suggestive of an important role of defects, likely related to the lack of a hydrostatic pressure transmitting medium, for pressures higher than 3 GPa.

Ground-State Charge-Density Distribution in a Crystal of the Luminescent ortho-Phenylenediboronic Acid Complex with 8-Hydroxyquinoline.

This contribution is devoted to the first electron density studies of a luminescent oxyquinolinato boron complex in the solid state. ortho-Phenylenediboronic acid mixed with 8-hydroxyquinoline in dioxane forms high-quality single crystals via slow solvent evaporation, which allows successful high resolution data collection (sin Î¸/λ = 1.2 Å-1) and charge density distribution modeling. Particular attention has been paid to the boron-oxygen fragment connecting the two parts of the complex, and to the solvent species exhibiting anharmonic thermal motion. The experiment and theory compared rather well in terms of atomic charges and volumes, except for the boron centers. Boron atoms, as expected, constitute the most electron-deficient species in the complex molecule, whereas the neighboring oxygen and carbon atoms are the most significantly negatively charged ones. This part of the molecule appears to be very much involved in the charge transfer occurring between the acid fragment and oxyquinoline moiety leading to the observed fluorescence, as supported by the time-dependent density functional theory (TDDFT) results and the generated transition density maps. TDDFT calculations indicated that p-type atomic orbitals contributing to the HOMO-1, HOMO, and LUMO play the major role in the lowest energy transitions, and enabled further comparison with the charge density features, which is discussed in details. Furthermore, the results confirmed the known fact the Q ligand character is most important for the spectroscopic properties of this class of complexes.

Multi-temperature study of potassium uridine-5'-monophosphate: electron density distribution and anharmonic motion modelling.

Uridine, a nucleoside formed of a uracil fragment attached to a ribose ring via a ß-N1-glycosidic bond, is one of the four basic components of ribonucleic acid. Here a new anhydrous structure and experimental charge density distribution analysis of a uridine-5'-monophosphate potassium salt, K(UMPH), is reported. The studied case constitutes the very first structure of a 5'-nucleotide potassium salt according to the Cambridge Structural Database. The excellent crystal quality allowed the collection of charge density data at various temperatures, i.e. 10, 100, 200 and 300 K on one single crystal. Crystal structure and charge density data were analysed thoroughly in the context of related literature-reported examples. Detailed analysis of the charge density distribution revealed elevated anharmonic motion of part of the uracil ring moiety relatively weakly interacting with the neighbouring species. The effect was manifested by alternate positive and negative residual density patterns observed for these atoms, which `disappear' at low temperature. It also occurred that the potassium cation, quite uniformly coordinated by seven O atoms from all molecular fragments of the UMPH- anion, including the O atom from the ribofuranose ring, can be treated as spherical in the charge density model which was supported by theoretical calculations. Apart from the predominant electrostatic interactions, four relatively strong hydrogen bond types further support the stability of the crystal structure. This results in a compact and quite uniform structure (in all directions) of the studied crystal, as opposed to similar cases with layered architecture reported in the literature.

Synthesis, structural characterization and computational studies of catena-poly[chlorido[µ3-(pyridin-1-ium-3-yl)phosphonato-κ3O:O':O'']zinc(II)].

Coordination polymers are constructed from two basic components, namely metal ions, or metal-ion clusters, and bridging organic ligands. Their structures may also contain other auxiliary components, such as blocking ligands, counter-ions and nonbonding guest or template molecules. The choice or design of a suitable linker is essential. The new title zinc(II) coordination polymer, [Zn(C5H5NO3P)Cl]n, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction and vibrational spectroscopy (FT-IR and FT-Raman). Additionally, computational methods have been applied to derive quantitative information about interactions present in the solid state. The compound crystallizes in the monoclinic space group C2/c. The four-coordinated ZnII cation is in a distorted tetrahedral environment, formed by three phosphonate O atoms from three different (pyridin-1-ium-3-yl)phosphonate ligands and one chloride anion. The ZnII ions are extended by phosphonate ligands to generate a ladder chain along the [001] direction. Adjacent ladders are held together via N-H...O hydrogen bonds and offset face-to-face π-π stacking interactions, forming a three-dimensional supramolecular network with channels. As calculated, the interaction energy between the neighbouring ladders is -115.2 kJ mol-1. In turn, the cohesive energy evaluated per asymmetric unit-equivalent fragment of a polymeric chain in the crystal structure is -205.4 kJ mol-1. This latter value reflects the numerous hydrogen bonds stabilizing the three-dimensional packing of the coordination chains.

Reply To: How Does Substitutional Doping Affect Visible Light Absorption in a Series of Homodisperse Ti11 Polyoxotitanate Nanoparticles--A Comment on the Band Gap Determination of the Fe(II) Cages.

A summary of the evidence based on spectroscopy, calculated density of states (DOS) and photo-electrochemistry, for electron transfer from the occupied Fe(2+) (d)-ß orbital located within the band gap of the [Ti4 O(OEt)15 (FeBr)] cluster, to its unoccupied Ti(d) orbitals is presented. The importance of the distinction between the concepts of band gap and HOMO-LUMO gap is emphasized.

How Does Substitutional Doping Affect Visible Light Absorption in a Series of Homodisperse Ti11 Polyoxotitanate Nanoparticles?

Homodisperse doped polyoxotitanate nanoclusters with formulae Ti11 (MX)O14 (OiPr)17 (M=Mn, Fe or Co; X=Cl, Br or I, OiPr=isopropoxide) display strongly dopant-dependent properties. Spectroscopic solution and reflectance measurements backed up by density of states and time-dependent DFT calculations based on the determined structures, show the prominent effect of FeX substitution by decreasing the HOMO-LUMO gap of the particles. The effect is attributed to the presence of an occupied Fe ß orbital halfway up the bandgap, leading to long-wavelength absorption with electron transfer to the titanium atoms of the cluster. Whereas the light absorption varies significantly with variation of the transition metal dopant, its dependency on the nature of the halogen atom or the change in dipole moment across the series is minor.