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1.
Chem Sci ; 15(32): 13074-13081, 2024 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-39148789

RESUMEN

The synthesis and ion-pair binding properties of a heteroditopic [2]catenane receptor exhibiting highly potent and selective recognition of sodium halide salts are described. The receptor design consists of a bidentate halogen bonding donor motif for anion binding, as well as a di(ethylene glycol)-derived cation binding pocket which dramatically enhances metal cation affinity over previously reported homo[2]catenane analogues. 1H NMR cation, anion and ion-pair binding studies reveal significant positive cooperativity between the cation and anion binding events in which cation pre-complexation to the catenane subsequently 'switches-on' anion binding. Notably, the heteroditopic catenane displayed impressive selectivity for sodium halide recognition over the corresponding potassium halides. We further demonstrate that the catenane is capable of extracting solid alkali metal salts into organic media. Crucially, the observed solution phase binding selectivity for sodium halides translates to superior functional extraction capabilities of these salts relative to potassium halides, overcoming the comparatively higher lattice enthalpies NaX > KX dictated by the smaller alkali metal sodium cation. This is further exemplified in competitive solid-liquid experiments which revealed the exclusive extraction of sodium halide salts from solid mixtures of sodium and potassium halide salts.

2.
Angew Chem Int Ed Engl ; : e202412097, 2024 Aug 13.
Artículo en Inglés | MEDLINE | ID: mdl-39136339

RESUMEN

A sulfonated tris(1-phenylpyrazolato)iridium(III) complex ([Ir(sppz)3]3-) serves as a proof-of-concept non-emissive enhancer of the widely used ECL detection system of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) with tri-n-propylamine (TPrA) co-reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi-excitation of the luminophore. Using self-interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)3]2+ ECL intensity using [Ir(sppz)3]3- was obtained without its concomitant emission. The most prominent enhancement (11-fold) occurred at low potentials associated with the 'indirect' co-reactant ECL pathway, which translated to between 2- and 6-fold enhancement when the luminophore was immobilised on microbeads as a general model for enhanced ECL assays.

3.
Chemistry ; 30(32): e202400071, 2024 Jun 06.
Artículo en Inglés | MEDLINE | ID: mdl-38570194

RESUMEN

Chiral Metal-Organic Frameworks (CMOFs) are a rapidly growing field reflecting their potential as selective and sensitive chemical sensors for chiral analytes. The highly tuneable nature of CMOFs enables the size, shape, and non-covalent interactions to be optimised towards specific analytes to engender strong intermolecular interactions and sensing responses. While CMOFs as chiral chemical sensor devices have been explored with electrochemical methods including differential pulse voltammetry (DPV), bipolar and chemiresistive sensing techniques, the CMOFs as chiral chemical sensors using spectroscopic methods has received significantly less attention. This review examines the synthesis of CMOFs for chemical sensors with spectroscopic methods such as photoluminescence, circular dichroism, and solid-state nuclear magnetic resonance with a view towards their incorporation into chemical sensor devices. Future directions of the field are highlighted for the generation of functional devices.

4.
Inorg Chem ; 61(17): 6641-6649, 2022 May 02.
Artículo en Inglés | MEDLINE | ID: mdl-35442030

RESUMEN

We investigate the effects of a broad array of external stimuli on the structural, spin-crossover (SCO) properties and nature of the elastic interaction within the two-dimensional Hofmann framework material [Fe(cintrz)2Pd(CN)4]·guest (cintrz = N-cinnamalidene 4-amino-1,2,4-triazole; A·guest; guest = 3H2O, 2H2O, and Ø). This framework exhibits a delicate balance between ferro- and antiferro-elastic interaction characters; we show that manipulation of the pore contents across guests = 3H2O, 2H2O, and Ø can be exploited to regulate this balance. In A·3H2O, the dominant antiferroelastic interaction character between neighboring FeII sites sees the low-temperature persistence of the mixed spin-state species {HS-LS} for {Fe1-Fe2} (HS = high spin, LS = low spin). Elastic interaction strain is responsible for stabilizing the {HS-LS} state and can be overcome by three mechanisms: (1) partial (2H2O) or complete (Ø) guest removal, (2) irradiation via the reverse light-induced excited spin-state trapping (LIESST) effect (λ = 830 nm), and (3) the application of external hydrostatic pressure. Combining experimental data with elastic models presents a clear interpretation that while guest molecules cause a negative chemical pressure, they also have consequences for the elastic interactions between metals beyond the simple chemical pressure picture typically proposed.

5.
Chem Sci ; 13(11): 3273-3280, 2022 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-35414869

RESUMEN

Visible light induced singlet nucleophilic carbenes undergo rapid [2 + 1]-cycloaddition with tethered olefins to afford unique bicyclo[3.1.0]hexane and bicyclo[4.1.0]heptane scaffolds. This cyclopropanation process requires only visible light irradiation to proceed, circumventing the use of exogenous (photo)catalysts, sensitisers or additives and showcases a vastly underexplored mode of reactivity for nucleophilic carbenes in chemical synthesis. The discovery of additional transformations including a cyclopropanation/retro-Michael/Michael cascade process to afford chromanones and a photochemical C-H insertion reaction are also described.

6.
Chem Commun (Camb) ; 58(28): 4512-4515, 2022 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-35302117

RESUMEN

A fluorescent, chiral coordination polymer (CP) with a novel topology has been synthesised using a dipyridyl ligand derived from 1,1'-bi-2-naphthol (BINOL). Enantioselectivity ratios up to 2.61 were obtained in fluorescence sensing studies with chiral analytes.


Asunto(s)
Polímeros , Ligandos , Espectrometría de Fluorescencia , Estereoisomerismo
7.
Cryst Growth Des ; 21(9): 4927-4939, 2021 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-34483749

RESUMEN

The propensity of molecular organic compounds to form stoichiometric or nonstoichiometric crystalline hydrates remains a challenging aspect of crystal engineering and is of practical relevance to fields such as pharmaceutical science. In this work, we address the propensity for hydrate formation of a library of eight compounds comprised of 5- and 6-membered N-heterocyclic aromatics classified into three subgroups: linear dipyridyls, substituted Schiff bases, and tripodal molecules. Each molecular compound studied possesses strong hydrogen bond acceptors and is devoid of strong hydrogen bond donors. Four methods were used to screen for hydrate propensity using the anhydrate forms of the molecular compounds in our library: water slurry under ambient conditions, exposure to humidity, aqueous solvent drop grinding (SDG), and dynamic water vapor sorption (DVS). In addition, crystallization from mixed solvents was studied. Water slurry, aqueous SDG, and exposure to humidity were found to be the most effective methods for hydrate screening. Our study also involved a structural analysis using the Cambridge Structural Database, electrostatic potential (ESP) maps, full interaction maps (FIMs), and crystal packing motifs. The hydrate propensity of each compound studied was compared to a compound of the same type known to form a hydrate through a previous study of ours. Out of the eight newly studied compounds (herein numbered 4-11), three Schiff bases were observed to form hydrates. Three crystal structures (two hydrates and one anhydrate) were determined. Compound 6 crystallized as an isolated site hydrate in the monoclinic space group P21/a, while 7 and 10 crystallized in the monoclinic space group P21/c as a channel tetrahydrate and an anhydrate, respectively. Whereas we did not find any direct correlation between the number of H-bond acceptors and either hydrate propensity or the stoichiometry of the resulting hydrates, analysis of FIMs suggested that hydrates tend to form when the corresponding anhydrate structure does not facilitate intermolecular interactions.

8.
Dalton Trans ; 50(37): 12821-12825, 2021 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-34498023

RESUMEN

A new metal-organic framework (MOF) containing a Mn(II) salen complex (BET surface area = 967 ± 6 m2 g-1) undergoes a reversible crystalline-to-amorphous transformation. Experimental studies and computational calculations show that the MOF is stable to a one-electron reduction at more anodic potentials than the corresponding discrete complex.

9.
Inorg Chem ; 60(17): 13658-13668, 2021 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-34428031

RESUMEN

A remarkably flexible, multifunctional, 2D coordination polymer exhibiting an unprecedented mode of reversible mechanical motion, enabling pores to open and close, is reported. Such multifunctional materials are highly sought after, owing to the potential to exploit coexisting electronic and mechanical functionalities that underpin useful technological applications such as actuators and ultrasensitive detectors. The coordination polymer, of composition Mn(F4TCNQ)(py)2 (F4TCNQ = 2,3,5,6-tetrafluoro-7,7,8,8-tetracycanoquinodimethane; py = pyridine), consists of Mn(II) centers bridged by F4TCNQ dianions and coordinated by py molecules that extend above and below the 2D network. Exposure of Mn(F4TCNQ)(py)2, in its collapsed state, to carbon dioxide results in a pore-opening process at a threshold pressure for a given temperature. In addition to carbon dioxide, a variety of volatile guests may be incorporated into the pores, which are lined with electron-rich F4TCNQ dianions. The inclusion of electron-deficient guests such as 1,4-benzoquinone, nitrobenzene, maleic anhydride, and iodine into the pores is accompanied by a striking color change associated with a new host-guest charge-transfer interaction and an improvement in the semiconductor behavior, with the iodine adduct showing an increase in conductivity of almost 5 orders of magnitude. Experimental and density functional theory calculations on this remarkable multifunctional material demonstrate a reduction in the optical band gap with increasing electron affinity of the guest.

10.
Faraday Discuss ; 231(0): 152-167, 2021 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-34251000

RESUMEN

Electroactive metal-organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure-function relationships that govern the charge transfer mechanisms is required. Chemical or electrochemical reduction of the framework [Zn(BPPFTzTz)(tdc)]·2DMF, hereafter denoted ZnFTzTz (where BPPFTzTz = 2,5-bis(3-fluoro-4-(pyridin-4-yl)phenyl)thiazolo[5,4-d]thiazole), generates mixed-valence states with optical signatures indicative of through-space intervalence charge transfer (IVCT) between the cofacially stacked ligands. Fluorination of the TzTz ligands influences the IVCT band parameters relative to the unsubstituted parent system, as revealed through Marcus-Hush theory analysis and single crystal UV-Vis spectroscopy. Using a combined experimental, theoretical and density functional theory (DFT) analysis, important insights into the effects of structural modifications, such as ligand substitution, on the degree of electronic coupling and rate of electron transfer have been obtained.

11.
Chem Commun (Camb) ; 57(64): 7938-7941, 2021 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-34286753

RESUMEN

Studies into the Cp*Rh(iii)-catalysed hydroarylation of alkenes with aryl acyl silanes led to the discovery of a new synthetic strategy to access unique silicon derived indene frameworks. Rather than protodemetalation of the metal enolate formed following insertion of an alkene into the aryl C-H bond, intramolecular aldol condensation of the acyl silane occurred to generate a series of 2-formyl- and 2-acetyl-3-silyl indenes. This represents only the second example of rhodium-catalysed C-H functionalisation employing acyl silanes as weakly coordinating directing groups and the intramolecular aldol condensation strategy was extended to access analogous silicon derived benzofurans.

12.
Chem Asian J ; 16(8): 890-901, 2021 Apr 19.
Artículo en Inglés | MEDLINE | ID: mdl-33709619

RESUMEN

Coordination polymers and metal-organic frameworks are prime candidates for general chemical sensing, but the use of these porous materials as chiral probes is still an emerging field. In the last decade, they have found application in a range of chiral analysis methods, including liquid- and gas-phase chromatography, circular dichroism spectroscopy, fluorescence sensing, and NMR spectroscopy. In this minireview, we examine recent works on coordination polymers as chiral sensors and their enantioselective host-guest chemistry, while highlighting their potential for application in different settings.

13.
Chemistry ; 27(16): 5136-5141, 2021 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-33543525

RESUMEN

Foremost, practical applications of spin-crossover (SCO) materials require control of the nature of the spin-state coupling. In existing SCO materials, there is a single, well-defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4-triazole-based trimers coordinated into 1D chains by [Au(CN)2 ]- and spaced by anions and exchangeable guests, underwent SCO defined by elastic coupling across multiple dimensional hierarchies. Detailed structural, vibrational, and theoretical studies conclusively confirmed that intra-trimer coupling was an order of magnitude greater than the intramolecular coupling, which was an order of magnitude greater than intermolecular coupling. As such, a clear hierarchy on the nature of elastic coupling in SCO materials was ascertained for the first time, which is a necessary step for the technological development of molecular switching materials.

14.
Chem Commun (Camb) ; 57(1): 85-88, 2021 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-33245087

RESUMEN

A 3-D FeII Hofmann-type framework material has been prepared which contains a three-connecting pyridyl-donor ligand with amide functionality and [Au(CN)2]- metallo-ligands. The FeII sites display a rare FeII(py)3(N[triple bond, length as m-dash]C)3 coordination environment, which we show for the first time to be conducive to spin crossover (SCO).

15.
Chem Commun (Camb) ; 56(94): 14829-14832, 2020 Nov 26.
Artículo en Inglés | MEDLINE | ID: mdl-33155589

RESUMEN

Chirality is a key aspect of amino acids and is essential for life. Here, a chiral metal-organic framework, S-Mg2dobpdc, is used to determine the chirality of three BOC protected amino acids (alanine, valine and proline) by 13C solid-state NMR with chemical shift differences of up to 1.3 ppm observed between enantiomers. The chiral sensitivity persists upon in situ deprotection of the amino acids by thermolysis of the BOC group.


Asunto(s)
Aminoácidos/química , Magnesio/química , Estructuras Metalorgánicas/química , Espectroscopía de Resonancia Magnética con Carbono-13 , Estereoisomerismo
16.
Inorg Chem ; 58(10): 7044-7053, 2019 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-31034214

RESUMEN

Semiquinoid radical bridging ligands are capable of mediating exceptionally strong magnetic coupling between spin centers, a requirement for the design of high-temperature magnetic materials. We demonstrate the ability of sulfur donors to provide much stronger coupling relative to their oxygen congeners in a series of dinuclear complexes. Employing a series of chalcogen donor-based bis(bidentate) benzoquinoid bridging ligands, the series of complexes [(TPyA)2Cr2(RL4-)]2+ (OLH4 = 1,2,4,5-tetrahydroxybenzene, OSLH4 = 1,2-dithio-4,5-dihydroxybenzene, SLH4 = 1,2,4,5-tetrathiobenzene, TPyA = tris(2-pyridylmethyl)amine) was synthesized. Variable-temperature dc magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange coupling between CrIII centers in these complexes, with exchange constants of J = -2.83(3) (OL4-), -2.28(5) (OSL4-), and -1.80(2) (SL4-) cm-1. Guided by cyclic voltammetry and spectroelectrochemical measurements, chemical one-electron oxidation of these complexes gives the radical-bridged species [(TPyA)2Cr2(RL3-•)]3+. Variable-temperature dc susceptibility measurements in these complexes reveal the presence of strong antiferromagnetic metal-semiquinoid radical coupling, with exchange constants of J = -352(10) (OL3-•), - 401(8) (OSL3-•), and -487(8) (SL3-•) cm-1. These results provide the first measurement of magnetic coupling between metal ions and a thiosemiquinoid radical, and they demonstrate the value of moving from O to S donors in radical-bridged metal ions in the design of magnetic molecules and materials.

17.
Chem Sci ; 10(5): 1392-1400, 2019 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-30809356

RESUMEN

Understanding charge transfer in redox-active metal-organic frameworks (MOFs) is of fundamental importance given the potential of these materials to be used in myriad applications including porous conductors, electrocatalysts and battery materials, amongst others. An important challenge is quantifying the spectroscopic features of these materials in order to elucidate their charge transfer properties. Herein, two topologically related Zn(ii) and Cd(ii) frameworks, [Zn2(DPPTzTz)2(SDC)2] (1-Zn) and [Cd2(DPPTzTz)2(SDC)2] (2-Cd) (where DPPTzTz = 2,5-bis(4-(4-pyridinyl)phenyl)thiazolo[5,4-d]thiazole and SDC = selenophene-2,5-dicarboxylate), incorporating cofacially stacked pairs of redox-active DPPTzTz ligands are presented. The differences in the through-space intervalence charge transfer properties of the mixed-valence forms of the two frameworks generated upon solid state spectroelectrochemical reduction are quantified using Marcus-Hush theory. Further, charge transfer theory is applied to calculate electron mobilities in both extended framework systems. A larger electronic coupling constant, H ab, of 118 cm-1 corresponding to an electron mobility, k, of 6.02 × 108 s-1 was observed for the Zn(ii) analogue compared to the Cd(ii) analogue (H ab = 61.2 cm-1 and k = 2.22 × 108 s-1) and was correlated primarily with the larger cofacial stacking distance and increasingly offset stacking geometry between DPPTzTz ligands in the latter. Establishing structure-activity relationships in electroactive MOFs, in addition to methods for quantifying their charge transfer properties, represents an important advance in fine tuning solid state materials for device applications.

18.
Chem Commun (Camb) ; 55(22): 3219-3222, 2019 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-30806425

RESUMEN

Industrial specifications require CO2 concentrations in natural gas below 50 ppm during liquefaction because of corrosion and CO2 freezing. Herein, we report a physisorbent (TIFSIX-3-Ni) that exhibits new benchmark CO2/CH4 selectivity and fast kinetics, thereby enabling one-step LNG processing to CO2 levels of 25 ppm.

19.
Chemistry ; 25(20): 5222-5234, 2019 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-30729591

RESUMEN

Reaction of the chloranilate dianion with Y(NO3 )3 in the presence of Et4 N+ in the appropriate proportions results in the formation of (Et4 N)[Y(can)2 ], which consists of anionic square-grid coordination polymer sheets with interleaved layers of counter-cations. These counter-cations, which serve as squat pillars between [Y(can)2 ] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size-shape complementarity leading to a strong interaction between host and guest for CO2 and CH4 . Single-crystal X-ray diffraction experiments indicate significant interactions between the host framework and discrete I2 or Br2 molecules. A series of isostructural compounds (cat)[MIII (X-an)2 ] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et4 N, Me4 N and X-an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et4 N)[Gd(can)2 ] and (Et4 N)[Dy(can)2 ] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et4 N)[Gd(can)2 ].

20.
Chem Commun (Camb) ; 55(10): 1454-1457, 2019 Jan 29.
Artículo en Inglés | MEDLINE | ID: mdl-30644471

RESUMEN

We report herein that the mode of entanglement in square lattice, sql, coordination networks formed by an extended bis-imidazole ligand, L, can be controlled by the solvent used during solvothermal synthesis. [ML2(NO3)2]n (M = Co, Ni) exhibit both parallel 2D → 2D interpenetration and, unusually, mixed entanglement (parallel-inclined 2D → 3D polycatenation).

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