The separation and detection of trace benzene in cyclohexane is a challenging task in the chemical industry due to its nearly identical physical properties. Herein, we report a tailored metal-organic framework (MOF), NIIC-66, which simultaneously addresses both challenges through a synergistic combination of molecular sieving and luminescent sensing. NIIC-66 exhibits exceptional selectivity for benzene over cyclohexane in the liquid phase, with record-high selectivity factors of 998 and 1929 for 10:100 and 1:100 benzene-cyclohexane mixtures, respectively. Practical application demonstrates the purging of benzene from 99.9% cyclohexane to achieve 99.999% purity. Furthermore, benzene adsorption induces a pronounced luminescence response, featuring a significant intensity enhancement and a bathochromic shift. The limit of detection for benzene in cyclohexane is 13 ppm, the lowest value reported to date for liquid-phase detection. Single-crystal X-ray diffraction and computational studies reveal that the exceptional performance arises from the framework's narrow slit-like pores and electron-deficient benzothiadiazole units, which facilitate strong π-π stacking interactions with benzene molecules, enabling both selective capture and luminescent sensing.

Three new Ni(II) coordination compounds with anions of 4,8-disulfo-2,6-naphthalenedicarboxylic acid (H4dsndc) and 1,2-bis(4-pyridyl)ethylene (bpe), differing in dimensionality and structure, were obtained: the molecular complex [Ni(H2O)52(bpe)](dsndc), the one-dimensional coordination polymer [Ni(H2O)4(bpe)](H2dsndc)·2H2O, and the two-dimensional coordination polymer [Ni(H2O)32(bpe)2(dsndc)]·2H2O. The structures of the compounds were determined by single-crystal X-ray diffraction analysis. The compound [Ni(H2O)4(bpe)](H2dsndc)·2H2O was obtained in chemically and phase-pure form and characterized by a standard set of physicochemical methods (powder X-ray diffraction, elemental and thermogravimetric analyses, and IR spectroscopy).

Two new anionic scandium(III)-organic frameworks based on 2,5-thiophendicarboxylate ligands have been synthesized, and their structure has been determined by the single-crystal X-ray diffraction analysis. Compound (H2NMe2)[Sc3(H2O)2(OH)2(tdc)4]·C4H8O2·H2O (1) (tdc2− = 2,5-thiophendicarboxylate, H2NMe2+ = dimethylammonium cation, C4H8O2 = 1,4-dioxane) represents a two-dimensional metal-organic framework with the AAA type arrangement of layers. Compound (Hdabco)[Sc3(OH)2(tdc)4]·DMF (2) (dabco = 1,4-diazabicyclo[2.2.2]octane, DMF = N, N-dimethylformamide) is a three-dimensional metal-organic framework with the channels of (4⋅5) Å2 occupied by guest DMF molecules and protonated dabco molecules acting as counterions. After optimizing the synthesis conditions, compound 2 has been obtained in a chemically and phase pure form and characterized by a complex of physicochemical methods of investigations such as powder X-ray diffraction, chemical and thermogravimetric analyses and IR spectroscopy. The stability of 2 in aqueous solutions, humid and dry atmosphere during at least a month has been confirmed by powder X-ray diffraction analysis. The exchange of Hdabco+ cations to various metal cations in aqueous solutions has been studied using 2 as an anionic adsorbent, revealing a pronounced affinity of this MOF towards Fe(III) ions with more than 50

Correction for 'Confinement of Cd(II) by 2,2'-bipyridyl: control of structural transformations and porosity in perfluorinated biphenyldicarboxylate MOFs' by Pavel V. Burlak et al., Dalton Trans., 2026, https://doi.org/10.1039/d5dt02607e.

Cadmium(II) can form complexes with coordination numbers 6 and 7, which makes them labile, especially with relatively weak ligands like perfluorinated carboxylates. Confining the coordination environment with chelating ligands such as 2,2'-bipyridyl (2,2'-bpy) is a promising approach to obtain complexes with more predictable geometry and stability. Using this strategy, MOFs with anions of octafluorobiphenyldicarboxylic acid (H2oFbpdc) were successfully synthesized in different alcohols. Compound [Cd(2,2'-bpy)(oFbpdc)]·CH3OH (1·MeOH) exhibits a 3D framework, whereas the other phases [Cd(2,2'-bpy)(oFbpdc)]·G (2·G, G = EtOH, iPrOH, tBuOH) adopt a layered structure. Thermal activation of all phases results in guest removal, yielding the non-porous phase [Cd(2,2'-bpy)(oFbpdc)] (2). Despite its non-porous nature, 2 undergoes a structural transformation upon CO2 adsorption into an open form with a specific surface area of 237 m2 g-1. This transformed phase shows good adsorption selectivity for binary C2H2/CH4 and CO2/CH4 mixtures.

Three new anionic three-dimensional metal-organic frameworks based on heterocyclic polycarboxylate ligands have been synthesized: (H2NMe2)3[Zn2{NaZn2}(dabco)2(tdc)6]center dot 4.5DMF center dot H2O (1, CCDC 2527083), (H2NMe2) [NaZn(fdc)2] (2, CCDC 2527084), (H2NMe2)[CdLi(btdc)2] (3, CCDC 2527085), where tdc2-= 2,5-thiophenedi-carboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane, DMF = N,N-dimethylformamide, fdc2-= 2,5-furanedicar-boxylate, btdc2-= 2,2 '-bithiophene-5,5 '-dicarboxylate. The structure of the compounds has been established by single crystal X-ray diffraction analysis; the chemical and phase purity of compounds 2 and 3 has been proved by elemental, thermogravimetric and powder X-ray diffraction analyses and IR spectroscopy. The luminescence excitation and emission spectra of the solid phases 2 and 3 have been recorded, and the quantum yields have been obtained. The influence of mono-, di-and trivalent metal cations on the luminescence intensity of the suspensions of the MOF 3 has been investigated, and the luminescence response of the MOF suspensions to the presence of Co(II) and Ni(II) has been revealed and studied quantitatively.

A series of mononuclear copper(I) complexes, [CuL(PPh3)Br], [CuL(PPh3)I] and [CuL(PPh3)(2)](PF6) (L = 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)pyrimidine), was synthesized. Free L exhibits bright fluorescence in the blue region (PLQY 29 %). The complexes demonstrate luminescence in the yellow-to-red region. Considerable emission quenching in [CuL(PPh3)Br] and [CuL(PPh3)I] (PLQY < 1 %) is contributed by the electron-poor heterocycles in the ligand structure, which favour the overstabilization of LUMO in the T-1 state, the decrease of HOMO-LUMO and S-0-T-1 gaps and, as a consequence, the increase of the ratio of non-radiative events. Instead, the introduction of the second PPh3 molecule in the coordination sphere of Cu+ ion on going from [CuL(PPh3)Br] and [CuL(PPh3)I] to [CuL(PPh3)(2)](PF6) causes the widening of the HOMO-LUMO and S-0-T-1 gaps, which in turn leads to the increase of PLQY up to 9 %.

Phenylene-based bis-oxamate polydentate ligands offer a unique opportunity for creating a large variety of coordination compounds, in which paramagnetic metal ions are strongly magnetically coupled. The employment of imino nitroxyl (IN) radicals as supplementary ligands confers numerous benefits, including the strong ferromagnetic interaction between Ni and IN. Furthermore, the chelating IN can act as a capping ligand, thereby impeding the formation of coordination polymers. In this study, we present the molecular and crystal structure and experimental and theoretical magnetic behavior of an exceptional neutral trinuclear complex [Ni(L3−)2(IN)3]∙5CH3OH (1) (L is N,N′-1,3-phenylenebis-oxamic acid; IN is [4,4,5,5-tetramethyl-2-(6-methylpyridin-2-yl)-4,5-dihydro-1H-imidazol-1-yl]oxidanyl radical) with a cyclic triangular arrangement. Moreover, in this compound three Ni2+ ions are linked by the two bis-oxamate ligands playing a rare tritopic function due to an unprecedented triple deprotonation of the related meta-phenylene-bis(oxamic acid). The main evidence of such a deprotonation of the ligand is the neutrality of the cluster, since there are no anions or cations compensating for its charge in the crystals of the compound. Despite the presence of six possible magnetic couplings in the trinuclear cluster 1, its behavior was reproduced with a high degree of accuracy using a three-J model and ZFS, under the assumption that the three different Ni-IN interactions are equal to each other, whereas only two equivalent-in-value Ni-Ni interactions were taken into account, with the third one being equated to zero. Our study indicates the presence of two opposite-in-nature types of magnetic interactions within the triangular core. DFT and CASSCF/NEVPT2 calculations were completed to support the experimental magnetic data simulation.

We report the discovery of remarkably short intermolecular Se & ctdot;Se contacts (3.242-3.751 & Aring;) and a novel supramolecular (Se)/(Se)\(Se)/(Se) zigzag pattern in Ni(ii) diselenophosphinate complexes. The monoclinic polymorph of [Ni(Se2PPh2)(2)], along with [Ni(Se2PPh2)(2)(Pz)(2)] and the 1D polymer [Ni(Se2PPPh2)(2)(3,3 '-bipy)](n), exhibit this zigzag pattern with one short (avg. 3.35 & Aring;) and two longer (avg. 3.68 & Aring;) Se & ctdot;Se contacts between adjacent NiP2Se4 units. In contrast, the orthorhombic [Ni(Se2PPh2)(2)] and the 1D polymer [Ni(Se2PPPh2)(2)(4,4 '-bipy)](n) display chain-like intermolecular Se & ctdot;Se contacts of about 3.51 & Aring;. Employing a multifaceted approach, we elucidate the nature of the interactions, distinguishing between the electrostatic and dispersion contributions. Using theoretical methods (DFT-DKH for geometry optimization; electron density, ESP, ELF, and SAPT0 for analysis), we find that short Se & ctdot;Se interactions (<90%& sum;r(vdW(Se & ctdot;Se))) are governed primarily by dispersion forces, whereas longer Se & ctdot;Se contacts (>90% & sum;r(vdW(Se & ctdot;Se))) are mainly attributed to electrostatic forces, typical of sigma-hole interactions. Notably, we document an unprecedented Se & ctdot;Se contact of 3.242 & Aring;, which, to our knowledge, is the shortest proven non-covalent Se & ctdot;Se interaction reported to date. This finding not only confirms the existence of Se & ctdot;Se interactions, but also highlights their potential strength and importance in coordination chemistry, an aspect that has not been thoroughly explored in previous studies.

The adsorption of methane, ethane, and their equimolar mixture in the mesoporous NIIC-20-Bu metal-organic framework (MOF) is investigated utilizing molecular simulations and artificial neural networks. To the best of knowledge, this is the first computational study of small alkanes sorbed in this particular MOF. Grand Canonical Monte Carlo simulations provided the adsorption isotherms of the aforementioned alkanes in NIIC-20-Bu at different temperatures. The simulation findings are compared with existing experimental sorption measurements showing reasonable quantitative and qualitative agreement. Predictive models based on artificial neural networks are developed incorporating simulation data and available experimental measurements in the training phase to predict the sorption isotherms of methane, ethane, and their equimolar mixture in NIIC-20-Bu mesoporous material with the minimum computational cost. 3D density profiles of sorbed methane and ethane are computed based on their positions in the simulation box of NIIC-20-Bu, as obtained from GCMC simulations. Moreover, the analysis of the aforementioned profiles highlighted preferred localization domains, siting motifs and interesting segregation phenomena of the sorbed methane, ethane molecules as pure components or in their equimolar mixture within the mesoporous crystal. The present findings highlight the potential applications of NIIC-20-Bu as an efficient adsorbent material.

Four new porous homochiral metal–organic frameworks (MOFs), [M2(camph)2(bpa)]∙Solv (M = Co(II), Ni(II), Cu(II) and Zn(II)), based on (+)-camphoric acid (H2camph) and 1,2-bis(4-pyridyl)ethane (bpa) were synthesized and characterized. The crystal structures of [Ni2(camph)2(bpa)] and [Zn2(camph)2(bpa)] were established by single-crystal X-ray diffraction analysis. Powder X-ray data prove the phase purity and isostructural nature of all four compounds. The thermal stability of [M2(camph)2(bpa)] was found to depend on the electronic configuration, as well as on the redox properties of the metal cation, and varied from 225 °C (M = Zn2+) to 375 °C (M = Ni2+). The reversible, solvent-induced sponge-like dynamics of the coordination frameworks was thoroughly investigated. Changes in the positions of reflexes, related to the length of the flexible bpa linker, were observed by powder XRD, pointing to transitions between an open-framework phase and a squeezed, non-porous phase in a crystal-to-crystal manner, while the integrity and connectivity of the coordination network were maintained. Size-selective adsorption from a benzene–cyclohexane 1:1 mixture on [Zn2(camph)2(bpa)] was studied by 1H NMR analysis. The benzene-favorable composition of guest molecules (C6H6:C6H12 = 5:1) occluded within the host crystalline sponge revealed a preferable adsorption affinity towards smaller benzene compared with larger cyclohexane. High framework stability in various solvents, as well as successful molecular separation in the liquid state, validates the potential utilization of chiral porous metal(II) camphorate MOFs in important stereoselective applications.

Синтезированы изоструктурные биядерные комплексы [Ln2L2(hfac)6] (Ln = Eu, Tb; hfac‒ - гексафторацетилацетонат-ион) взаимодействием [Ln(hfac)3(H2O)2] c 3,6-бис(дифенилфосфинил)пиридазином (L). По данным РСА, в комплексах два фрагмента Ln(hfac)3 связаны двумя O,O´-бидентатно-мостиковыми лигандами L, при этом координационный полиэдр Ln@O8 имеет геометрию треугольного додекаэдра. Комплексы Eu3+ и Tb3+ проявляют характерную лантаноид-центрированную фотолюминесценцию в твердой фазе при 297 K с квантовыми выходами люминесценции 31 и 2% и временами жизни возбужденных состояний 707 и 30 мкс соответственно, что свидетельствует о более эффективной сенсибилизации лигандным окружением люминесценции иона Eu3+ по сравнению с Tb3+.

Three new three-dimensional (3D) metal-organic frameworks [M2(ttdc)2(dabco)] (M = Zn(II), 1-Zn; Cu(II), 1-Cu; and Zn/Cu, 1-ZnCu) based on thieno[3,2-b]thiophene-2,5-dicarboxylate (ttdc2-) were synthesized and characterized by a combination of physicochemical methods (single crystal X-ray diffraction, powder X-ray diffraction, chemical and thermogravimetric analyses and IR spectroscopy). 1-Cu demonstrated permanent porosity (Vpore = 0.790 cm3 g-1 and SBET = 1725 m2 g-1) and significant CO2, CH4, C2H2, C2H4 and C2H6 gas uptakes under ambient conditions. The adsorption selectivities for gas mixtures, calculated by IAST, were 10.8 (10.7), 14.6 (9.4), 1.7 (1.6) and 1.5 (1.6) for the equimolar gas mixture compositions CO2/N2, C2H6/CH4, C2H6/C2H4 and C2H6/C2H2 at 1 bar and 273 K (298 K), respectively. The mixed-metal compound 1-ZnCu was prepared by a crystal-to-crystal ion exchange metathesis reaction from 1-Zn with a 52% degree of ion substitution, confirmed by energy-dispersive X-ray spectroscopy, optical microscopy and single crystal X-ray diffraction analysis.

Small bifunctional molecules are attractive for use as models in different areas of knowledge. How can their functional groups interact in solids? This is important to know for the prediction of the physical and chemical properties of the materials based on them. In this study, two new hydrogen-bonded organic frameworks (HOFs) based on sterically demanding molecular compounds, bis(1-hydroxy-2-methylpropane-2-aminium) sulfate (1) and 2-methyl-4-oxopentan-2-aminium hydrogen ethanedioate hydrate (2), were synthesized and fully characterized by means of FTIR and NMR spectroscopies, as well as by X-ray powder diffraction and thermogravimetric analyses. Their molecular and crystal structures were established through single-crystal X-ray diffraction analysis. It was shown that both compounds have a layered structure due to the formation of a 2D hydrogen-bonding network, the layers being linked by systematically arranged Van der Waals contacts between the methyl groups of organic cations. To unveil some dependencies between the chemical nature of bifunctional molecules and their solid structure, Hirschfeld surface (HS) analysis was carried out for HOFs 1, 2, and their known congeners 1-hydroxy-2-methylpropan-2-aminium hemicarbonate (3) and 1-hydroxy-2-methylpropan-2-aminium (1-hydroxy-2-methylpropan-2-yl) carbamate (4). HS was performed to quantify and visualize the close intermolecular atomic contacts in the crystal structures. It is clearly seen that H–H contacts make the highest contributions to the amino alcohol based compounds 1, 3 and 4, with a maximal value of 65.2% for compound 3 having CO32− as a counterion. A slightly lower contribution of H–H contacts (64.4%) was found for compound 4, in which the anionic part is represented by 1-hydroxy-2-methylpropan-2-yl carbamate. The significant contribution of the H–H contacts in the bifunctional moieties is due to the presence of a quaternary carbon atom with a short three-carbon chain.

Coordination polymers [Mg(EtOH)3(H2O)(1,3-tFBDC)]·EtOH (1), [Mg(MeOH)2(1,2-tFBDC)] (2), [Mg(H2O)2(EtOH)2Mg(1,2-tFBDC)2] (3), and [Mg(EtOH)2(1,4-tFBDC)] (4) are obtained in the interaction of magnesium hydroxide with various isomers of tetrafluorobenzene dicarboxylic acid (phthalic, isophthalic, and terephthalic; H2tFBDC) in alcohol solutions (MeOH or EtOH). The compositions and structures of these compounds are determined by single crystal X-ray diffraction. Compound 1 is a chain coordination polymer; compounds 2–4 have layered structures.

An original series of 1D, 2D and 3D networks based on group 11 metal ions was synthesized using tris(pyrazin-2-ylmethyl)phosphine (L1) and bis(pyrazin-2-ylmethyl)phenylphosphine (L2). The reaction of L1 with CuI results in either 1D chains [Cu2I2(L1)2]n or 2D networks [Cu2I2(L1)]n, while the treatment of L1 and L2 with [Ag(MeCN)4]PF6 in aqueous MeCN produces 3D cationic frameworks [Ag(L1)]n(PF6)n and [Ag(L2)(H2O)]n(PF6)n, respectively. Finally, 1D polymer [Ag3Au(L1)2(MeCN)3]n(BF4)4n containing {AuAg2} cluster units was assembled from phosphine L1, Au(tht)Cl and AgBF4. QTAIM analysis of [Cu2I2(L1)]n and [Ag3Au(L1)2(MeCN)3]n(BF4)4n polymers revealed the presence of pronounced metallophilic Cu∙∙∙Cu and Au∙∙∙Ag interactions. Moreover, the CuI-based networks exhibited a yellow and red emission, which was tentatively attributed to thermally activated delayed fluorescence (TADF) of (M + X)LCT type.

New porous metal-organic frameworks (MOF) [Cd7(Btdc)7(Bpa)2(Dmf)2(H2O)2]·15Dmf·2H2O (I) and [Cd7(Btdc)7(Bpe)2(Dmf)2]·15Dmf·3H2O (II) (H2Btdc is 2,2′-bithiophene-5,5′-dicarboxylic acid, Bpa is 1,2-bis(4-pyridyl)ethane, Bpe is 1,2-bis(4-pyridyl)ethylene, and Dmf is N,N-dimethylformamide) are synthesized under solvatothermal conditions. The structures and compositions of the compounds are determined by single-crystal X-ray diffraction (XRD) (CIF files ССDС nos. 2364290 (I) and 2364289 (II)) and confirmed by powder XRD, elemental analysis, thermogravimetry, and IR spectroscopy. Compound I has a 2D structure based on the heptanuclear discrete building unit Cd7 with the linear structure. Compound II is a 3D MOF in which the Cd7 building units are linked into a continuous chain motif due to additional interactions. The formation of either discrete or continuous chains is directly related to the nature of the N-donor bridging ligand (Bpe or Bpa). Compounds I and II have open structures with the accessible volume about 50

Получено пять новых металл-органических координационных полимеров на основе 4,8-дисульфо-2,6-нафталиндикарбоновой кислоты (H4dsndc) [Cd2(dsndc)(dmf)6] (1), [Mn2(dsndc)(dmf)6] (2), [Zn2(dsndc)(dmf)6] (3), [Co2(dsndc)(dmf)6] (4) и [Cd2(dsndc)(dma)6] (5) (dmf = N,N-диметилформамид, dma = N,N-диметилацетамид), четыре из которых (1–4) являются изоструктурными слоистыми координационными полимерами. Структуры всех соединений установлены методом монокристального рентгеноструктурного анализа. Соединения 1-3 и 5 получены в химически- и фазовочистом виде и охарактеризованы стандартным комплексом физико-химических методов (РФА, ИК, ТГА и CHN). Для соединения 3 записаны спектры возбуждения и испускания фотолюминесценции и получен квантовый выход, который составил 18 %.

alpha-Ketoglutarate dependent nonheme halogenases catalyze regioselective functionalization of aliphatic C-H bonds via H abstraction by the ferryl site of the [X-FeIV=O] intermediate, followed by radical rebound to an adjacent halogen ligand X at the same Fe center. Herein we report biomimetic nonheme Mn complexes, possessing two labile cis-alpha coordination sites and capable of catalyzing the enantioselective azidation of C(sp3)-H groups. Proper ligand environment of the active sites imposes steric constraints on HO-Mn rebound, thus accounting for preferential C-radical rebound to the adjacent N3-Mn ligand. Such mechanism of selectivity control is analogous to that operating in the prototypical alpha-ketoglutarate-dependent nonheme iron halogenases.

Supramolecular adducts of lanthanide complexes with cucurbituril, [{Eu(1-x)Nd(1+x)(H2O)(5)(NO3)}(2) CB[6]](NO3)(4)HNO36H(2)O (x = 0.5, -0.5), are prepared by heating a mixture of dissolved lanthanide nitrates and cucurbit[6]uril. According to the single-crystal XRD data for 1 and 2, the metal is connected to the macrocycle through the bidentate coordination of oxygen atoms of cucurbit[6]uril portals to the lanthanide(III) cations, thus leading to the formation of a molecular complex. In the crystal, the [{Ln(H2O)(5)(NO3)}(2)(CB[6])](4+) cations are interconnected by a system of hydrogen bonds. The compounds are shown to be isostructural and are characterized by a number of physicochemical methods: IR spectroscopy, powder XRD, and elemental analysis. Their luminescence spectra are recorded.