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The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm-ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O 2 , CO 2 , N 2 , opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO 2 physisorption, allowing the co-detection of CO and CO 2 . In this work, PCN-222, a stable Zr-based MOF made from Ni(TCPP) with natural vacancies, has been used as a porous matrix for the grafting of electron-poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN-222 was observed. At 1 atm, the adsorbed CO (g) volumes measured for the best materials were 12.15 cm 3  g -1 and 14.01 cm 3  g -1 for CoCorr2@PCN-222 and CoCorr3@PCN-222 respectively, and both materials exhibited high CO chemisorption and selectivity against O 2 , N 2 , and CO 2 at low pressure due to the highest energy of the chemisorption process vs physisorption., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

89 Zr-immunoPET is a hot topic as 89 Zr cumulates the advantages of 64 Cu and 124 I without their drawbacks. We report the synthesis of a model ligand of a chiral bioconjugable tetrahydroxamic chelator combining the desferriferrioxamine B siderophore and 1-hydroxy-2-piperidone ((PIPO)H), a chiral cyclic hydroxamic acid derivative, and the study by NMR spectroscopy of its zirconium complex. Nuclear Overhauser effect measurements (ROESY) indicated that the complex exists in the form of two diastereomers, in 77 : 23 ratio, resulting from the combination of the central chiralities at the 3-C of the (PIPO)H component and at the Zr 4+ cation. The 44 lowest energy structures out of more than 1000 configurations/conformations returned by calculations based on density functional theory were examined. Comparison of the ROESY data and the calculated interatomic H⋅⋅⋅H distances allowed us to select the most probable configuration and conformations of the major complex., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

227 Th is a promising radioisotope for targeted α-particle therapy. It produces 5 α-particles through its decay, with the clinically approved 223 Ra as its first daughter. There is an ample supply of 227 Th, allowing for clinical use; however, the chemical challenges of chelating this large tetravalent f -block cation are considerable. Using the CD20-targeting antibody ofatumumab, we evaluated chelation of 227 Th 4+ for α-particle-emitting and radiotheranostic applications. Methods: We compared 4 bifunctional chelators for thorium radiopharmaceutical preparation: S-2-(4-Isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane tetraacetic acid ( p -SCN-Bn-DOTA), 2-(4-isothicyanatobenzyl)-1,2,7,10,13-hexaazacyclooctadecane-1,4,7,10,13,16-hexaacetic acid ( p -SCN-Bn-HEHA), p -isothiacyanatophenyl-1-hydroxy-2-oxopiperidine-desferrioxamine (DFOcyclo*- p- Phe-NCS), and macrocyclic 1,2-HOPO N -hydroxysuccinimide (L804-NHS). Immunoconstructs were evaluated for yield, purity, and stability in vitro and in vivo. Tumor targeting of the lead 227 Th-labeled compound in vivo was performed in CD20-expressing models and compared with a companion 89 Zr-labeled PET agent. Results: 227 Th-labeled ofatumumab-chelator constructs were synthesized to a radiochemical purity of more than 95%, excepting HEHA. 227 Th-HEHA-ofatumumab showed moderate in vitro stability. 227 Th-DFOcyclo*-ofatumumab presented excellent 227 Th labeling efficiency; however, high liver and spleen uptake was revealed in vivo, indicative of aggregation. 227 Th-DOTA-ofatumumab labeled poorly, yielding no more than 5%, with low specific activity (0.08 GBq/g) and modest long-term in vitro stability (<80%). 227 Th-L804-ofatumumab coordinated 227 Th rapidly and efficiently at high yields, purity, and specific activity (8 GBq/g) and demonstrated extended stability. In vivo tumor targeting confirmed the utility of this chelator, and the diagnostic analog, 89 Zr-L804-ofatumumab, showed organ distribution matching that of 227 Th to delineate SU-DHL-6 tumors. Conclusion: Commercially available and novel chelators for 227 Th showed a range of performances. The L804 chelator can be used with potent radiotheranostic capabilities for 89 Zr/ 227 Th quantitative imaging and α-particle therapy., (© 2023 by the Society of Nuclear Medicine and Molecular Imaging.)

A novel cobalt corrole bearing 4-vinylphenyl groups at the 5,10,15- meso -positions of the macrocycle has been synthesized from tris(4-bromophenyl)corrole using a Suzuki coupling reaction. The spectral and electrochemical properties are reported in CH 2 Cl 2 along with its ability to form a highly stable six-coordinate complex and cross-linked corrole-based polymer in a 59% yield.

Five isostructural microporous supramolecular architectures prepared by H-bonded assembly between the hexa-anionic complex [Zr 2 (Ox) 7 ] 6- (Ox=oxalate, (C 2 O 4 ) 2- ) and tripodal cations (H 3 -TripCH 2 -R) 3+ with R=H, CH 3 , OH and OBn (Bn=CH 2 Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH 3 ) has also been successfully explored, providing a unique example of three-component H-bonded porous framework. The resulting SPA-1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 Å. Influence of R groups on the sorption properties of these materials is evidenced through CO 2 and H 2 O vapor sorption/desorption experiments, as well as with I 2 capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H-bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Cationic amidotitanocene complexes [Cp 2 Ti(NPhAr)][B(C 6 F 5 ) 4 ] (Cp=η 5 -C 5 H 5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H 3 BNHMe 2 results in fast homolytic Ti-N cleavage to give [Cp 2 Ti(H 3 BNHMe 2 )][B(C 6 F 5 ) 4 ] (3). 1 a-c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H 2 activation key step was disclosed using the Activation Strain Model (ASM)., (© 2021 Wiley-VCH GmbH.)

Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (L Cy,Pr )H 2 , of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2-11 by potentiometry and visible absorption spectrophotometry. Equilibrium constants and absorption spectra for three [UO 2 (DFB)H h ] (h-1)+ (h = 1-3) and five [UO 2 (L Cy,Pr ) l H h ] (2+h-2l)+ (-1 ≤ h ≤ 1 for l = 1 and h = 0-1 for l = 2) solution complexes were determined at 25.0 °C and I = 0.1 M KNO 3 . Similar studies for the Fe 3+ /(L Cy,Pr ) 2- system revealed the formation of five species having [Fe(L Cy,Pr )] + , [Fe(L Cy,Pr )OH], [Fe(L Cy,Pr )(OH) 2 ] - , [Fe(L Cy,Pr ) 2 H], and [Fe 2 (L Cy,Pr ) 3 ] compositions. Then, the ability of DFB, (L Cy,Pr )H 2 , and citrate to solubilize either U or Pu from pitchblende-rich soils (soils 1 and 2) or freshly plutonium-contaminated soils (LBS and PG) was evaluated by performing batch extraction tests. U was extracted significantly only by citrate after a day. After one week, the amount of U complexed by citrate only slightly exceeded that measured for the siderochelates, following the order citrate > (L Cy,Pr )H 2  ≥ DFB ≈ H 2 O, and were comparatively very low. Pu was also more efficiently extracted by citrate than by DFB after a day, but only by a factor of ~2-3 for the PG soil, while the Pu concentration in the supernatant after one week was approximately the same for both natural chelators. It remained nearly constant for DFB between the 1st and 7th day, but drastically decreased in the case of citrate, suggesting chemical decomposition in the latter case. For the Fe-rich soils 1 and 2, the efficiencies of the three chelators to solubilize Fe after a day were of the same order of magnitude, decreasing in the order DFB > citrate > (L Cy,Pr )H 2 . However, after a week DFB had extracted ~1.5 times more Fe, whereas the amount extracted by the other chelators stayed constant. For the less Fe-rich LBS and PG soils contaminated by Pu, the amounts of extracted Fe were higher, especially after 7 days, and the DFB outperformed citrate by a factor of nearly 3. The higher capacity of the hexadentate DFB to extract Pu in the presence of Fe and its lower ability to mobilize U qualitatively agree with the respective complexation constant ratios, keeping in mind that both Pu-containing soils had a lower iron loading. Noticeably, (L Cy,Pr )H 2 has roughly the same capacity as DFB to solubilize U, but it mobilizes less Fe than the hexadentate siderophore. Similarly, citrate has the highest capacity to extract Pu, but the lowest to extract Fe. Therefore, compared to DFB, (L Cy,Pr )H 2 shows a better U/Fe extraction selectivity and citrate shows a better Pu/Fe selectivity., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The quantification of specific gases among thousands of VOCs (Volatile Organic Compounds) present in the human breath at the ppm/ppb level can be used to evidence the presence of diseases in the human body. The detection of these biomarkers in human exhaled breath through a noninvasive approach is an important field of research that is still attracting significant attention to this day. A portable device working at room temperature and usable directly on exhaled breath samples is still a challenge requiring a sensing material with high performances. The rich composition of the human breath implies that the sensing material must be highly selective and sensitive (ppm/ppb) in high relative humidity (RH) conditions and preferably at room temperature. The present work intends to provide a review on recent works in this application field through the use of porous materials and discuss the importance of Metal Organic Frameworks (MOFs) for such application. MOFs are highly porous crystalline materials often used for gas detection and capture, thus raising questions about their potential for detection in exhaled breath.

The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide ( BIPP ) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac -fashion, and the central phosphorus atom enables the formation of d 0 -d 10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus-metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu-Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P-P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium ( TP ) cations; (ii) the P-P bonds are normal covalent ( i.e. not dative) in both BIPP and TP ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Three mono-CN ligated anionic cobalt A 3 -triarylcorroles were synthesized and investigated as to their spectroscopic and electrochemical properties in CH 2 Cl 2 , pyridine (Py), and dimethyl sulfoxide (DMSO). The newly synthesized corroles provide the first examples of air-stable cobalt corroles with an anionic axial ligand and are represented as [(Ar) 3 CorCo III (CN)] - TBA + , where Cor is the trivalent corrole macrocycle, Ar is p -(CN)Ph, p -(CF 3 )Ph, or p -(OMe)Ph, and TBA + is the tetra- n -butylammonium (TBA) cation. Multiple redox reactions are observed for each mono-CN derivative with a key feature being a more facile first oxidation and a more difficult first reduction in all three solvents as compared to all previously examined corroles with similar meso- and β-pyrrole substituents. Formation constants (log K ) for conversion of the five-coordinate mono-CN complex to its six-coordinate bis-CN form ranged from 10 2.8 for Ar = p -(OMe)Ph to 10 4.7 for Ar = p -(CN)Ph in DMSO as determined by spectroscopic methodologies. The in situ generated bis-CN complexes, represented as [(Ar) 3 CorCo III (CN) 2 ] 2- (TBA + ) 2 , and the mixed ligand complexes, represented as [(Ar) 3 CorCo III (CN)(Py)] - TBA + , were also investigated as to their electrochemical and spectroscopic properties. UV-visible spectra and electrode reactions of the synthesized mono-CN derivatives are compared with the neutral mono-DMSO cobalt corrole complexes and the in situ generated bis-CN and bis-Py complexes, and the noninnocent (or innocent) nature of each cobalt corrole system is addressed. The data demonstrate the ability of the CN - axial ligand(s) to stabilize the high-valent forms of the metallocorrole, leading to systems with innocent macrocyclic ligands. Although a number of six-coordinate cobalt(III) corroles with N-donor ligands were characterized in the solid state, a dissociation of one axial ligand readily occurs in nonaqueous solvents, and this behavior contrasts with the high stability of the currently studied bis-CN adducts in CH 2 Cl 2 , pyridine, or DMSO. Linear free energy relationships were elucidated between the meso -phenyl Hammett substituent constants (Σσ) and the measured binding constants, the redox potentials, and the energy of the band positions in the mono-CN and bis-CN complexes in their neutral or singly oxidized forms, revealing highly predictable trends in the physicochemical properties of the anionic corroles.

A new series of cobalt A 3 -triarylcorroles were synthesized and the compounds examined as to their electrochemical and spectroscopic properties in CH 2 Cl 2 or dimethyl sulfoxide (DMSO) containing 10 different anions added to the solution in the form of tetrabutylammonium salts. The investigated anions were PF 6 - , BF 4 - , HSO 4 - , ClO 4 - , Br - , I - , Cl - , OAc - , F - , OTs - , and CN - , all but three of which were found to facilitate reduction of the cobalt corrole in dilute CH 2 Cl 2 solutions, as determined by a combination of UV-vis spectroscopy and spectroelectrochemistry. The synthesized corroles are represented as (Ar) 3 CorCo(DMSO), where Ar is a meso -phenyl group containing one of 10 different electron-donating or -withdrawing substituents. The axial DMSO ligand was found to dissociate in dilute (10 -5 M) CH 2 Cl 2 solutions, but this was not the case at the higher electrochemical concentration of 10 -3 M, where the investigated corroles exhibit a rich redox reactivity, undergoing up to five reversible one-electron-transfer reactions under the different solution conditions. The reversible half-wave potentials for generation of the singly oxidized corroles varied by over 1.0 V with a change in the electron-donating or -withdrawing meso -phenyl substituents and type of anion added to the solution, ranging from E 1/2 = 0.83 V in one extreme to -0.42 V in the other. Much smaller shifts in the potentials (on the order of ∼210 mV) were observed for the reversible first reduction as a function of changes of the anion and/or corrole substituents, with the only exception being in the case of CN - , where the E 1/2 values in CH 2 Cl 2 ranged from +0.08 V in solutions containing 0.1 M TBAClO 4 to >-1.8 V upon the addition of CN - .

Porous organic polymers (POPs), known for their high surface area and porosity, were prepared starting from tetraphenyl tetrahedral-shaped building blocks and corrole macrocyclic linkers either as free bases or cobalt complexes. This synthetic method allowed us to construct new porous frameworks with high carbon monoxide adsorption properties. Two synthetic strategies were developed for incorporating cobalt corroles into the porous matrix. The first method is based on the copper-free Sonogashira cross-coupling reaction between a free base diodo-corrole with a tetrahedral shaped derivative followed by cobalt complexation of the resulting material, leading to POP-CorCo-1. The second strategy consists of preparing POP-CorCo-2 by directly using in the coupling reaction the metalated cobalt corrole temporarily protected by two ammine ligands at the axial position. The design principles as well as the relationship between the structure and the selective CO adsorption performance are presented. The adsorption capacities and selectivities of CO were calculated from a multisite Langmuir isotherm model and using IAST theory. Spectroscopic studies (NMR, FTIR, UV-visible), kinetic sorption measurements and microscopic analyses made possible to provide a fairly complete description of the structure of the POPs, their porosity and the nature of solid-gas interactions. The POPs prepared by both methods show a high permanent porosity and outstanding CO sorption properties with a high selectivity over N2, O2 and CO2, up to 15 700, 4000 and 1800, respectively. The two POP-CorCo therefore offer confined molecular spaces for ascertaining a high accessibility of the metallocorrole active sites for gas binding on the cobalt atom, thus featuring high potential for applications in selective capture or sensing of CO versus N2, O2 and CO2.

Diamondoids, sp 3 -hybridized nanometer-sized diamond-like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp 3 -C-based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO 2 and NH 3 gases. This carbon-based gas sensor technology allows reversible NO 2 detection down to 50 ppb and NH 3 detection at 25-100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p-type sensing properties are achieved from devices based on primary phosphine-diamantanol, in which high specific area (ca. 140 m 2  g -1 ) and channel nanoporosity derive from H-bonding., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tame d 0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d 1 precursors with [Cp 2 Fe][BPh 4 ]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d 0 complexes, whereas dπ-pπ repulsion prevents such interactions in the d 1 complexes. In addition, CH-π interactions were observed in several complexes, both in solution and in the solid state, between the phosphido ligand and the phosphane arm. The d 0 complexes were found to be light sensitive, and decompose through Ti-P bond homolysis to give Ti III species. A naked d 0 phosphidotitanocene cation has been trapped by reaction with diphenylacetylene, yielding a Ti/P frustrated Lewis pair (FLP), which was found to be less reactive than a previously reported Zr analog., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central cobalt ion, the electroactive conjugated macrocycle, and the electroactive meso-nitrophenyl groups are all discussed in terms of solvent binding and the number of the nitrophenyl groups and other substituents on the meso-nitrophenyl rings of the compounds.

Iron(III) and uranyl complexes of N-methylacetohydroxamic acid (NMAH) have been investigated by mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. A comparison between IRMPD and theoretical IR spectra enabled one to probe the structures for some selected complexes detected in the gas phase. The results show that coordination of Fe 3+ and UO 2 2+ by hydroxamic acid is of a very similar nature. Natural bond orbital analysis suggests that bonding in uranyl complexes possesses a slightly stronger ionic character than that in iron complexes. Collision-induced dissociation (CID), IRMPD, and 18 O-labeling experiments unambiguously revealed a rare example of the U═O bond activation concomitant with the elimination of a water molecule from the gaseous [UO 2 (NMA)(NMAH) 2 ] + complex. The U═O bond activation is observed only for complexes with one monodentate NMAH molecule forming a hydrogen bond toward one "yl" oxygen atom, as was found by DFT calculations. This reactivity might explain oxygen exchange observed for uranyl complexes.

A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate) 3 ] 3- , which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1 nm-large pores interconnected in 3D with large solvent-accessible void (53 %). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good selectivity of the porous material for the halogenated acids. The gathered results, including a series of guest@SPA-2 crystal structures and HRMAS-NMR spectra, suggest that the efficient sorption exhibited by the material relies not only on an acid-base interaction. The facile release of these guest molecules under neutral conditions makes this SPA a carrier of acidic molecules., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to ∼90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMes 2 (Mes = 2,4,6-trimethylphenyl) and ClBCy 2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides 5a,b in yields over 95%. Direct assembling of tert-butylated boryl cyclopentadienides with MCl 2 (M = Fe, Co) selectively leads to 1,1'-planar chiral ferrocenes 6a,b and cobaltocene 7. To shed light into the diastereoselective formation of 6a, DFT calculations were performed. The potential energy surface was scrutinized so as to identify and compare its diastereoisomers and conformers. This stereoselectivity is attributed to minimized steric repulsions between the tert-butyl and the BMes 2 groups in the eclipsed conformation of the racemic diastereoisomers. The X-ray structures of boryl diene 2a and diboryl ferrocene 6a are reported. The electronic structure of cobaltocene 7 was analyzed by EPR and DFT calculations. The spin density of this unique open-shell complex is mainly localized on the Co center, but significant spin density is also found on the boron atoms, indicating substantial delocalization of the unpaired electron over the Lewis acid moieties. Consistently, the singly occupied molecular orbital is a combination of a Co-centered 3d orbital with π(BC) orbitals on each CpBMes 2 rings. There is only weak, if any, direct M···B interaction in 6 and 7.

The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.86(2) and 9.63(5) for NMAH and NMA(-), respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemical shifts by density functional theory (DFT), which accurately reproduced the experimental data, turned out to be a much more reliable method than the direct computation of the relative energy for each conformer. The Z ⇌ E interconversion dynamics was probed at 300 K in D2O by 2D exchange-correlated spectroscopy (EXSY), affording the associated rate constants [kZE=9.0(2) s(-1) and kEZ=3.14(5) s(-1) for NMAH, kZE=0.96(3) s(-1) and kEZ=0.10(2) s(-1) for NMA(-)] and activation barriers at 300 K [ΔG(≠)ZE=68.0 kJ mol(-1) and ΔG(≠)EZ=70.6 kJ mol(-1) for NMAH, ΔG(≠)ZE=73.6 kJ mol(-1) and ΔG(≠)EZ=79.2 kJ mol(-1) for NMA(-)]. For the first time, mono- and bis-chelated uranium(VI) complexes of NMA(-) have been isolated. Crystals of [UO2(NMA)(NO3)(H2O)2] and [UO2(NMA)2(H2O)] have been characterized by X-ray diffractometry, infrared and Raman spectroscopies., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Hydrogen-bond assembly of tripod-like organic cations [H3 -MeTrip](3+) (1,2,3-tri(4'-pyridinium-oxyl)-2-methylpropane) and the hexa-anionic complex [Zr2 (oxalate)7 ](6-) leads to a structurally, thermally, and chemically robust porous 3D supramolecular framework showing channels of 1 nm in width. Permanent porosity has been ascertained by analyzing the material at the single-crystal level during a sorption cycle. The framework crystal structure was found to remain the same for the native compound, its activated phase, and after guest resorption. The channels exhibit affinities for polar organic molecules ranging from simple alcohols to aniline. Halogenated molecules and I2 are also taken up from hexane solutions by this unique supramolecular framework., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The molecular complexes K4[Zr(DBQ)4] and K4[Zr(CA)4], where DBQ(2-) and CA(2-) stand respectively for deprotonated dihydroxybenzoquinone and chloranilic acid, are reported. The anionic metal complexes consist of Zr(IV) surrounded by four O,O-chelating ligands. Besides the preparation and crystal structures for the two complexes, we show that in the solid state the DBQ complex forms a 3-D open framework (with 22% accessible volume) that undergoes a crystal-to-crystal phase transition to a compact structure upon guest molecule release. This process is reversible. In the presence of H2O, CO2, and other small molecules, the framework opens and accommodates guest molecules. CO2 adsorption isotherms show that the framework breathing occurs only when a slight gas pressure is applied. Crystal structures for both the hydrated and guest free phases of K4[Zr(DBQ)4] have been investigated.

Metal-organic frameworks constructed by self-assembly of metal ions and organic linkers have recently been of great interest in the preparation of porous hybrid materials with a wide variety of functions. Despite much research in this area and the large choice of building blocks used to fine-tune pore size and structure, it remains a challenge to synthesise frameworks composed of polyamines to tailor the porosity and adsorption properties for CO(2). Herein, we describe a rigid and microporous three-dimensional metal-organic framework with the formula [Zn(2)(L)(H(2)O)]Cl (L=1,4,7-tris(4-carboxybenzyl)-1,4,7-triazacyclononane) synthesised in a one-pot solvothermal reaction between zinc ions and a flexible cyclic polyaminocarboxylate. We have demonstrated, for the first time, that a porous rigid framework can be obtained by starting from a flexible amine building block. Sorption measurements revealed that the material exhibited a high surface area (135 m(2) g(-1)) and was the best compromise between capacity and selectivity for CO(2) over CO, CH(4), N(2) and O(2); as such it is a promising new selective adsorbent for CO(2) capture., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The present study reports the synthesis and rational design of porous structured materials by using a templating method. A tetraethoxysilylated tripodal tetraamine (TREN) was covalently incorporated in a silica framework with a double imprint: A surfactant template and a metal ion imprint. The presence of a cationic surfactant (CTAB) endowed the material with a high porosity, and the tripodal or square-pyramidal topology of the ligand was preserved thanks to the use of the silylated Cu(II) complex. After removal of the surfactant and de-metalation, the incorporated tetraamine was quantitatively complexed by CuCl(2) and the material has shown after thermal activation that a reversible binding of O(2) on the metal ions occurred. This chemisorption process was monitored by UV/Vis and EPR spectroscopies, and the Cu:O(2) adduct was postulated to be an end-on mu-eta(1):eta(1)-peroxodicopper(II) complex bridged by a chloride ion. The Cu(I)-active species, formed during the activation step, were fully recovered during several O(2) binding cycles. The high reactivity of the copper complexes and the room-temperature stability of the dioxygen adduct were explained by the fine adaptability of the tripodal ligand to different geometries, the confinement of the active sites in the hybrid silica that protect them from degradation by a control of the metal-ion microenvironment, as well as the short-range lamellar order of the copper complexes in the framework.

Single- as well as multi-anchored cyclam-functionalized silica samples have been prepared by grafting amorphous silica gel (K60) and mesostructured silica (SBA-15) with silylated cyclam precursors bearing one, two, or four triethoxysilyl groups, respectively ascribed to cyclam-mono, cyclam-di, and cyclam-tetra. Their reactivity toward copper(II) has been thoroughly investigated in aqueous solution and discussed with respect to the number of arms tethering the ligand to the silica surface and the structural ordering of the adsorbent in terms of capacity, long-term stability, and speed of access to the binding sites. Less-than-complete metal ion uptake was always observed, even in excess of cyclam groups with respect to solution-phase Cu(II), suggesting lower stability of immobilized complexes relative to those in solution. Therefore, the number of arms attaching cyclam moieties to the silica walls (one, two, or four) was found to dramatically affect the binding properties of these hybrids toward copper(II), revealing significantly larger capacities when reducing the number of arms (less rigidity constraints in the macrocycle). In parallel, multiarm tethering resulted in better chemical resistance toward degradation as evidenced by UV-visible monitoring of Cu-cyclam complexes in solution (i.e., more ligand leaching from the adsorbent for singly tethered cyclam). On the other hand, electron spin resonance (ESR) experiments did not evidence significant differences between complexes bearing one, two, or four alkyl arms, since all Cu(II)-cyclam surface complexes were found to be hexacoordinated with a strong equatorial ligand field. Comparison of amorphous gels and mesostructured materials indicates that the binding properties of the adsorbents were hardly influenced by their level of ordering, suggesting that accessibility to the binding sites was not the limiting factor. Some advantage belonging to mesostructured adsorbents was however observed with respect to the rate of access to the active centers at pH values close to neutrality (due to faster mass transport), but this was no more the case when operating at lower pH values where the formation of the Cu-cyclam complex became the rate-determining step, as pointed out by electrochemistry.

Molecule-based solids represent a rare opportunity to combine, adjust, and interrelate structural and physical functionalities to develop multifunctional materials. Here we report on a series of porous supramolecular magnets whose magnetic properties are related to their sorption state. A family of magnets of the formula [{Mn(HL)(H2O)}2Mn{Mo(CN)7}2].2H2O have been obtained by assembling the heptacyano-metalate building unit {Mo(CN)7}4- with Mn(II) in the presence of protonated N,N-dimethylalaninol (L) as ligand, the latter being either as a racemic mixture or as a chiral R- or S-enantiomer. The resulting magnets possess an open framework structure and exhibit a TC with a switching behavior (TC = 85 K <--> 106 K) as a function of the hydration state. Moreover, chiral magnets are formed with the optically active ligands. The H2O and gas (N2, CO2, CO) sorption features, the magnetic behavior of both the hydrated and dehydrated magnets, and the crystal structures of the hydrated chiral (S) and racemic magnets are described.

Twenty-one hybrid materials incorporating cobalt(III) corrole complexes were synthesized by a sol-gel process or by grafting the metallocorrole onto a mesostructured silica of the SBA-15 type. All the materials show an almost infinite selectivity for carbon monoxide with respect to dinitrogen and dioxygen in the low-pressure domain where the chemisorption phenomenon is predominant. This peculiar property is of prime importance for an application as a CO sensor. The selectivity slightly decreases at high pressures where nonselective physisorption phenomena mainly occur. The percentage of active sites for CO chemisorption ranges from 22 to 64 %. This low percentage may be attributable to interactions between the cobalt(III) corroles with silanol or siloxane groups remaining at the surface of the materials which prevent further coordination of the CO molecule. Notably, the most efficient materials are those prepared in the presence of a protecting ligand (pyridine) during the gelation or the grafting process. The removal of this ligand after the gelation process releases a cavity around the cobalt ion that favors the coordination of a carbon monoxide molecule. The CO adsorption properties of the SBA-15 hybrid were not affected over a period of several months thus indicating a high stability of the material. Conversely, the xerogel capacities slowly decrease owing to the evolution of the material structure.

We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

Most commercially available CO detectors are based upon metal oxides or electrochemical cell technologies. None of these approaches use the selective adsorption of CO gas on a molecular complex. Conversely, cobalt(III) corroles can bind small gaseous molecules allowing them for an application as sensing components for gas detectors. Here we describe the ability of cobalt corroles to selectively coordinate carbon monoxide vs. dinitrogen and dioxygen. The coordination properties were determined in the solid state and the adsorption characteristics were compared to those of the reference compound (To-PivPP)Fe(1,2-Me2Im), known for its remarkable CO binding properties. The adsorption data evidence that the selectivity, affinity and capacity of the cobalt(III) corroles for CO are larger than those of the porphyrin complex. However, from a chemical point of view, the selectivity of cobalt(III) corroles for CO vs. O2 is infinite since these derivatives do not bind O2 while (To-PivPP)Fe(1,2-Me2Im) does with an M value (PO2(1/2)/PCO(1/2)) equal to 51. In this manuscript we also show that the affinity of cobalt(III) corroles for CO is closely related to the Lewis acid character of the central cobalt(III) ion and therefore to the nature of the substituents at the periphery of the corrole macroring.

[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure.