Rigid Ligand Research Articles

Ligand mediated self-assembly of cobalt nanoclusters for tunable supercapacitors

Self-assembly of thiolated cobalt-based nanoclusters was achieved by a simple and one-step synthesis process towards the development of a tunable hybrid supercapacitor. Here, we report the wet chemical synthesis of self-assembly of cobalt nanoclusters (CoNCs) using three different thiols namely glutathione (GS), 3-mercapto propyl sulfonate (MPS) and 3-mercapto propionic acid (MPA) protected individually. The variation in the capping ability of the thiolate ligands brings the proximal changes in the optical, structural and electrochemical properties. In CoNCs, the structural and morphological changes that evolved from the obtained GS-CoNCs, MPS-CoNCs, and MPA-CoNCs were confirmed using UV–vis spectroscopy, XRD, and TEM analysis. The stability of CoNCs and binding states of cobalt metal were determined using TG and XPS analysis respectively. The divergence in the rigidifying nature of various thiolated cobalt nanoclusters significantly influences their capacitance ability for energy storage via altering the porosity and electron transfer characteristics. The rigid dense multifunctional ligands like GS facilitate the electron-hole hopping process in the nano-pockets available in GS, which enhances the energy storage capability and diffusion among ligand-metal-ligand chains. Wherein, the other two ligands MPS and MPA show comparatively lower supercapacitance activities due to diverse functionality and rigidify. The charge-discharge studies explore the supercapacitor behaviour of GS, MPS and MPA-protected CoNCs with the specific capacitance of 540, 494 and 358 F g−1 respectively at the current density of 1 A g−1.

Preorganization Effects on Eu(III) Ion Coordination by Dipyridyl-Phenanthroline Ligands: A Combined Experimental and Theoretical Analysis.

Although 1,10-phenanthroline has been proven to hold a strong complexing capacity for f-block elements and their derivatives have been applied in many fields, research on more highly or completely rigid phenanthroline ligands is still rare due to the challenging syntheses. Here, we reported three tetradentate ligands 2,9-di(pyridin-2-yl)-1,10-phenanthroline (L1), 12-(pyridin-2-yl)-5,6-dihydroquinolino[8,7b][1,10]phenanthroline (L2), and 5,6,11,12-tetrahydrobenzo[2,1-b:3,4-b']bis([1,10]phenanthroline) (L3) with increasing preorganization on the side chain; among which, L3 is fully preorganized. Their complexation reactions with Eu(III) were systematically investigated by electrospray ionization mass spectrometry (ESI-MS), UV-vis titrations, and single-crystal structures. It is found that all three ligands form only 1:1 M/L complexes with Eu(III). The single-crystal structures revealed that the three ligands hold similar coordination modes, while their stability constants determined by UV-vis titrations were L3 (4.80 ± 0.01) > L2 (4.38 ± 0.01) > L1 (3.88 ± 0.01). This trend is supported not only by the thermodynamic stability of rigid ligands compared to free ligands but also by the conclusion that rigid ligands exhibit faster reaction rates (lower energy barrier) than free ligands kinetically. This work is helpful in providing theoretical guidance for the subsequent development of highly preorganized chelating ligands with strong coordination ability and high selectivity for f-block elements.

2,5-Thiophenedicarboxylic Acid Bridging Hexameric CeIII-Substituted Selenotungstate and Its Application for Detecting Mucin 1.

The development of polyoxometalate chemistry not only is derived from the continuous discovery of novel polyoxometalates (POMs) but also stems from the exploitation of their new functionalities. In this work, we obtained a rigid sulfur-containing heterocyclic ligand-linking aggregate [N(CH3)4]10Na6H6[Ce8(H2O)26W8(HTDA)2(TDA)2O20][SeW4O18]2[SeW9O33]4·112H2O (1) (H2TDA = 2,5-thiophenedicarboxylic acid). Its polyanionic unit consists of one [Ce4(H2O)13W4O10(HTDA)(TDA)O10]18+ cluster and two kinds of Keggin-type [SeW4O18] and [SeW9O33] segments. It is noteworthy that H2TDA ligands not only work as connectors to link two symmetrical {[Ce4(H2O)13W4(HTDA)(TDA)O10][SeW4O18][SeW9O33]2}11- units but also function as ornaments to graft to the polyanionic backbone. Furthermore, 1 and 3,4-ethylenedioxythiophene (EDOT) were deposited on the glassy carbon electrode (GCE) by the electropolymerization (EPM) method, resulting in a 1-poly(3,4-ethylenedioxythiophene) (1-PEDOT) composite film, which can provide sufficient binding sites to immobilize Au nanoparticles (Au NPs). Hereafter, the Au NPs-immobilized 1-PEDOT modified electrode (Au/1-PEDOT/GCE) was used to construct an electrochemical aptasensor to detect mucin 1, showing a low detection limit of 29.5 fM in the Tris solution. This work not only demonstrates that rigid heterocyclic ligands are beneficial for the creation of novel rare-earth-substituted selenotungstate hybrids but also provides more enlightenment for POM-based materials used for electrochemical detection of cancer markers.

Reticular access to triptycene-based cationic metal–organic frameworks for protein-bound uremic toxins sorption

P-cresyl sulfate (pCS) and indoxyl sulfate (IS), a class of protein-bound uremic toxins, cannot be effectively cleared through hemodialysis treatment due to their strong binding to human serum albumin, posing a potential risk of cardiovascular disease in patients with chronic renal failure. Herein, we designed and prepared novel cationic metal–organic frameworks (MOFs), denoted as ZJU-X18, for the efficient removal of pCS and IS. A triptycene-based rigid trigonal prismatic ligand was utilized to link with Ag+ to yield a rare 4-fold interpenetrated MOF with abundant hydrophobic channels, affording high sorption capacity, excellent selectivity, and decent recyclability toward uremic toxins. Furthermore, the anion-exchange process between ZJU-X18 and uremic toxins is verified through density functional theory (DFT) calculations. This study provides a proactive example of the rational design of cationic MOFs from the perspective of reticular chemistry and demonstrates their promising application in uremia treatment.

Heteroleptic Cu(I) complex with vapochromism and its application as electrochromic material

Heteroleptic Cu(I) complex with vapochromism and its application as electrochromic material

Facile Heck coupling synthesis and characterization of a novel tris(4-(pyridine-4-vinyl)phenyl)methylsilane tridentate core

Aromatic rigid ligands with carboxylate, phosphate, or pyridyl terminals are highly important today for application in the manufacturing of metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and other supramolecular structures. Aromatic rigid ligands give rigidity to MOFs and COFs materials. In addition, building units are important in that their judicious selection can result in a 2-D or 3-D framework with moderate or high surface area. Most aromatic linkers are based on carbon centres which are associated with a negative impact on the environment. However, in contrast, silicon-based centres are scarce and benign to the environment, even though they can be prepared facilely via metathesis. Here, we report the facile preparation of a new tris (4-(pyridine-4-vinyl)phenyl) methylsilane using the classical Heck coupling reaction. The bridging ligand was synthesized via the standard Heck coupling of 4-vinylpyridine with tris(4-bromophenyl)(methyl)silane.

Non-Templated Assembly of D5h-Symmetric Pd5L10 Rings by Precise Ligand Angle Adjustment.

We report a series of Pd(II)nL2n coordination rings for which nuclearity is controlled by the binding angle of the corresponding bis-monodentate bridging ligands. Judicious choice of the angle within a family of rather rigid ligands allowed for the first-time to synthesize a homoleptic five-membered Pd5L10 ring that does not require any template to form. We demonstrate that control over the ring size is maintained both in the solid-, solution-, and gas-phase. Two X-ray structures of five-membered rings from ligands with ideal angles (yielding a perfect pentagonal ring) vs. suboptimal angles (resulting in a highly distorted structure) illustrate the importance of the correct ligand geometry. A mathematical model for estimating the expected ring size based on the ligand angle was derived and DFT computations show that ring-strain is the major factor determining the assembly outcome.

Isolable Dipyrromethene‐Based Heavier Group 14 and 15 Element Complexes

AbstractBoron‐dipyrromethenes (BODIPYs) have attracted much attention owing to their unique properties and widespread applications; however, the incorporation of the heavier group 14 and 15 elements in the rigid dipyrromethene ligands remains limited. Herein, the dipyrromethene‐based heavier group 14 and 15 element complexes, tin‐dipyrromethene (SNDIPY, 1) and arsenic‐dipyrromethene (ASDIPY, 2), which are direct analogues of BODIPY, have been facilely synthesized and isolated in moderate yields. Both compounds have been investigated by NMR, UV‐vis absorption, photoluminescence spectroscopy, cyclic voltammogram, X‐ray crystallography, as well as theoretical studies. Both compounds exhibit green photoluminescence. Notably, SNDIPY 1 is air‐stable and compound 2 represents the first isolable and structurally characterized ASDIPY.

Dynamic Fluorescent Metal–Organic Frameworks Utilizing a Flexible Saddle‐Like 3D Linker

AbstractDesigning single‐component fluorochromic metal–organic frameworks (MOFs) with multiple stages presents a significant challenge in the field of functional and smart MOFs. In this study, this challenge is successfully addressed by designing and synthesizing a novel ligand called cyclooctatetrathiophene‐tetrapyridine (COTTTP), and incorporating it into 3D MOFs known as Zn/Cd‐COTTTP. By exploiting the intrinsic properties of COTTTP, specifically its ability to undergo geometry changes from a bent form to a more planar form, both COTTTP as an individual molecule and the resulting Zn/Cd‐COTTTP MOFs exhibit similar fluorochromic behavior. This behavior manifests as a color change from yellow to orange to red. Characterization techniques such as single crystal X‐ray diffraction, Fourier transform infrared spectroscopy, solid‐state UV–vis and near‐infrared spectroscopy, and X‐ray photoelectron spectroscopy are employed to investigate and confirm the geometry change of COTTTP within the MOF structures. Furthermore, the introduction of an auxiliary rigid ligand to the system is explored, which effectively restricts the geometry change of COTTTP and subsequently diminishes the fluorochromic behavior. This work sheds new light on the design and application of smart porous materials, particularly in the realm of single‐component fluorochromic MOFs. The successful incorporation of COTTTP and the understanding of its geometry change provide insights into the development of functional and responsive MOFs for various applications.

A facile strategy of designing a new crystalline cobalt metal–organic framework as a new efficient and robust heterogeneous catalyst for olefin oxidation reaction

A novel three-dimensional (3D) metal-organic compound Co3(BDC)3(DMF)2(H2O)4.2DMF (DMF= N,N-dimethylformamide; BDC= 1,4-benzenedicarboxylate) (Co-BDC (1)) has been synthesized under solvothermal method using Co2+ salt and BDC as a rigid ligand. The material was structurally characterized by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR), thermogravimetric (TGA), inductively coupled plasma (ICP), and elemental (CHN) techniques. Oxidation of some olefins was evaluated with tert‑butyl hydroperoxide (TBHP) in acetonitrile in the presence of Co-BDC (2) (activated Co-BDC (1)) as a heterogeneous catalyst. Among the substrates used for the oxidation reaction, desirable conversions of 97 %, 81.6 %, and 76 % were obtained for cyclooctene, 1-hexene, and norbornene, respectively. Finally, the catalyst was recycled and reused (four times) without a remarkable decrease in the catalytic activity.

Water-stable Cu-based coordination polymer for ratiometric fluorescence detection of riboflavin

Riboflavin was first isolated from milk and widely used in food, biological and pharmaceutical fields. Accurate detection of riboflavin content is of great significance for the treatment of related diseases and the supervision of food/drug quality. In this paper, a 1D chain copper-based coordination polymer with excellent water stability was synthesized by hydrothermal method using rigid ligand 1,10-phenanthroline and flexible ligand 1,4-phenylenedioxydiacetic acid, named Cu-phen-PEDA. Based on the Förster resonance energy transfer (FRET) and dynamic quenching detection mechanism, the emission spectrum of Cu-phen-PEDA overlaps with the absorption spectrum of riboflavin. As an energy donor in this case, Cu-phen-PEDA significantly increases the fluorescence intensity of riboflavin (energy acceptor), while simultaneously decreasing its own fluorescence intensity, which is an effective proportional-building strategy. In the lower concentration range, riboflavin can be specifically recognized by ratiometric fluorescence with a good linear relationship, and the detection limit is as low as 23 nM. The potential aspects of its specificity, stability, reusability and practical application were explored.

Preparative and Catalytic Properties of MoVI Mononuclear and Metallosupramolecular Coordination Assemblies Bearing Hydrazonato Ligands.

A series of polynuclear, dinuclear, and mononuclear Mo(VI) complexes were synthesized with the hydrazonato ligands derived from 5-methoxysalicylaldehyde and the corresponding hydrazides (isonicotinic hydrazide (H2L1), nicotinic hydrazide (H2L2), 2-aminobenzhydrazide (H2L3), or 4-aminobenzhydrazide (H2L4)). The metallosupramolecular compounds obtained from non-coordinating solvents, [MoO2(L1,2)]n (1 and 2) and [MoO2(L3,4)]2 (3 and 4), formed infinite structures and metallacycles, respectively. By blocking two coordination sites with cis-dioxo ligands, the molybdenum centers have three coordination sites occupied by the ONO donor atoms from the rigid hydrazone ligands and one by the N atom of pyridyl or amine-functionalized ligand subcomponents from the neighboring Mo building units. The reaction in methanol afforded the mononuclear analogs [MoO2(L1-4)(MeOH)] (1a-4a) with additional monodentate MeOH ligands. All isolated complexes were tested as catalysts for cyclooctene epoxidation using tert-butyl hydroperoxide (TBHP) as an oxidant in water. The impact of the structure and ligand lability on the catalytic efficiency in homogeneous cyclooctene epoxidation was elucidated based on theoretical considerations. Thus, dinuclear assemblies exhibited better catalytic activity than mononuclear or polynuclear complexes.

Rare Earth alb-MOFs: From Synthesis to Their Deployment for Amine-Sensing Application in Aqueous Media.

The pursuit of developing sensors, characterized by their fluorescence-intensity enhancement or "turn-on" behavior, for accurately detecting noxious small molecules, such as amines, at minimal levels remains a significant challenge. Metal-organic frameworks (MOFs) have emerged as promising candidates as sensors as a result of their diverse structural features and tunable properties. This study introduces the rational synthesis of a new highly coordinated (6,12)-connected rare earth (RE) alb-MOF-3, by combining the nonanuclear 12-connected hexagonal prismatic building units, [RE9(μ3-O)2(μ3-X)12(OH)2(H2O)7(O2C-)12], with the 6-connected rigid trigonal prismatic extended triptycene ligand. The resulting Y-alb-MOF-3 material is distinguished by its high microporosity and Brunauer-Emmett-Teller surface area of approximately 1282 m2/g, which offers notable hydrolytic stability. Remarkably, it demonstrates selective detection capabilities for primary aliphatic amines in aqueous media, as evidenced by fluorescence turn-on behavior and photoluminescence (PL) titration measurements. This work emphasizes the potential of MOFs as sensors in advancing their selectivity and sensitivity toward various analytes.

Enhancing Conductivity of Silver Nanowire Networks through Surface Engineering Using Bidentate Rigid Ligands.

Solution processable metallic nanomaterials present a convenient way to fabricate conductive structures, which are necessary in all electronic devices. However, they tend to require post-treatments to remove the bulky ligands around them to achieve high conductivity. In this work, we present a method to formulate a post-treatment free conductive silver nanowire ink by controlling the type of ligands around the silver nanowires. We found that bidentate ligands with a rigid molecular structure were effective in improving the conductivity of the silver nanowire networks as they could maximize the number of linkages between neighboring nanowires. In addition, DFT calculations also revealed that ligands with good LUMO to silver energy alignment were more effective. Because of these reasons, fumaric acid was found to be the most effective ligand and achieved a large reduction in sheet resistance of 70% or higher depending on the nanowire network density. The concepts elucidated from this study would also be applicable to other solution processable nanomaterials systems such as quantum dots for photovoltaics or LEDs which also require good charge transport being neighboring nanoparticles.

Ruthenium polyhydrides supported by rigid PCP pincer ligands: dynamic behaviour and reactions with CO2.

Two rigid β-elimination immune PCcarbeneP pincer ligands, differing in their electron donor properties by variation of the substitution pattern on the aromatic linker arms, were complexed to ruthenium to form the dichlorides LRRuCl2 (R = H or NMe2). These compounds were converted to hydrido chlorides by treatment with dihydrogen (H2) and a base. By converting to tert-butoxide derivatives in situ under an atmosphere of H2, the poly hydride PCalkylP complexes LHRRu(H)3 compounds were generated. In these complexes, H2 has added across the RuC bond in the PCcarbeneP starting materials. The polyhydrides are dynamic in solution and extensive NMR studies helped to elucidate the speciation and fluxional processes operative in this dynamic system. The polyhydride complexes react rapidly with CO2 to give the PCcarbeneP formato hydride complexes LRRu(H)-κ2-O2CH. For R = H, the 1,2-hydride shift from the anchoring alkyl of the PCalkylP carbon to the metal is reversible, but for R = NMe2 it is irreversible. The CO2 incorporated into the formato ligand of these compounds exchanges with free CO2via a bimolecular mechanism that is more rapid for R = NMe2 than for R = H; plausible explanations for this observation are proffered. Experiments designed to evaluate the efficacy of the R = NMe2 formato hydride complex as a catalyst precursor for CO2 hydrogenation to formate salts reveal poor performance in comparison to state-of-the-art ruthenium-based catalysts. This is due primarily to the precipitation of a dimeric μ-κ2-κ1-CO3 carbonate complex that is not an active catalyst for the reaction.

Triptycene-based diiron(II) mesocates: spin-crossover in solution.

Triptycene-based diiron(II) and dizinc(II) mesocates were obtained using a novel rigid ligand with two pyridylbenzimidazole chelating units fused into the triptycene scaffold. Studies on the diiron(II) assembly in solution showed that the complex undergoes thermal-induced one-step spin-crossover with T1/2 at 243 K (Evans method).

Theoretical investigations into the bonding and separation properties of non-rigid, partially rigid, and rigid ligands derived from Et-Tol-PTA with trivalent lanthanides and actinides.

The separation of trivalent actinide elements from lanthanide elements represents one of the most formidable challenges within the context of nuclear waste partitioning and transmutation (P&T) processes. Consequently, we embarked on a systematic investigation aimed at elucidating the bonding properties and thermodynamic behavior of a N-ethyl-N-tolyl-2-amide-1,10-phenanthroline (Et-Tol-PTA) ligand in conjunction with trivalent actinide and lanthanide elements. This investigation involved the utilization of various density functional theory (DFT) methods and a comparative analysis between small-core pseudopotential basis sets and all-electron basis sets. It was found that well-performing results were achieved using the PBE0 functional in both bond length and thermodynamic energy calculations, with minimal impact being exerted by the basis set on the results. Furthermore, an exploration was carried out into the bonding and thermodynamic properties of trivalent actinides and lanthanides with ligands derived from Et-Tol-PTA, encompassing non-rigid (La), partially rigid (Lb, Lc), and rigid (Ld) ligands. Thermodynamically, advantages in the separation of Am(III)/Eu(III) were exhibited by Lb and Lc ligands, while excellent performance in the separation of Am(III)/Cm(III) was demonstrated by the La ligand. Analyses conducted using quantum theory of atoms in molecules (QTAIM), reduced density gradient (RDG), and natural bond orbital (NBO) methodologies revealed the presence of partial covalent character in the bonds between oxygen (O) and metal (M), as well as between nitrogen (N) and metal (M), with a higher degree of covalent character being observed in O-Am and N-Am bonds compared to O-Cm/Eu and N-Cm/Eu interactions.

An octahedral coordination cage with six Fe(III) centers as a T1 MRI probe.

The incorporation of multiple Fe(III) centers bridged by rigid ligands into a coordination cage represents a powerful approach for designing effective MRI contrast agents. In this context, an octahedral coordination cage with six high-spin Fe(III) centers is shown to be water soluble, robust towards dissociation and has effective relaxivity as a T1 MRI probe in solution and in mice.

Modulating magnetic anisotropy in linear tetranuclear dysprosium(III) complexes via coordinated anions.

We report the synthesis, structures, and magnetic properties of two novel linear tetranuclear complexes with the general formula [Dy4(Hheb)2(heb)4X2(MeOH)4] (X- = NO3-, OAc-; H2heb = (E)-N'-(1-(2-hydroxyphenyl)ethylidene)benzohydrazide, OAc- = acetate). The rigid ligands (Hheb-/heb2-) incorporate phenoxide groups and bridge the Dy3+ ions in an unusual tetranuclear linear assembly. Notably, we demonstrate through magnetic measurements and theoretical calculations how the anion (X) coordinated at the peripheral Dy3+ centers acts as a switch, significantly changing the magnetic anisotropy of the entire complex. This control over magnetic anisotropy through the selection of the coordinated anion offers a promising avenue for tailoring the functionality of single-molecule magnets.

Electrocatalytic hydrogen evolution of MOF-derived materials based on conjugated or unconjugated ligands

Two organic ligands, one rigid and one flexible, were used to construct two cobalt MOFs, respectively. The HER performance of the derived materials based on the rigid ligand is better than that of derivatives based on the flexible organic ligand.