Ligand Modification Research Articles

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis

AbstractThe development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand‐modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand‐modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure‐performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Lead-free perovskite Cs3Sb2Cl3I6 via additive engineering for enhancing output performance of optoelectronic and triboelectric coupled nanogenerator

Perovskite-based triboelectric nanogenerators (TENGs) are emerging as promising renewable energy devices that achieve optoelectronic and triboelectric coupling on their own to improve electric output. Nevertheless, the coupled electric output is susceptible to low triboelectric and optoelectronic properties due to internal defects of perovskites and limitations in film quality. Hence, in this work, additive engineering was used to introduce poly(ethylene oxide) (PEO) polymer into lead-free perovskite Cs3Sb2Cl3I6 precursor to modulate the crystal growth and passivate the crystal defects and optimize film quality, which can synergistically optimize optoelectronic and triboelectric properties. Under illumination, the open-circuit voltage (VOC) and the short circuit current (ISC) of unmodified Cs3Sb2Cl3I6-based TENG are 116V and 11.4 μA through optoelectronic and triboelectric coupling effects, respectively. In contrast, the VOC and ISC of TENG based on Cs3Sb2Cl3I6 modified by PEO are up to 184V and 19.1 μA, respectively, which increases by 58.62% and 67.54%. The maximum power density can reach 2.13Wm-2. Most importantly, the PEO-modified Cs3Sb2Cl3I6-based TENG exhibits excellent stability, which can maintain 90.9% of its initial triboelectric output within 40 days. This work declares that ligand modification is an effective strategy to improve the electric output of coupled TENG, providing a new perspective for achieving high-performance perovskite-based TENG, and photothermal therapy by monitoring both human motion and environmental light intensity.

Cu(I)‐Induced ‘Click Reaction’ Involving Coordination and Covalent Assembly of Hybrid Borates for the Electrocatalytic CO2 Reduction

AbstractThe design and synthesis of hybrid borates by the organic ligand modification method are urgent and undeveloped areas of research. It is difficult to directly integrate organoboronic acids within inorganic borate chemistry by adopting the traditional preparation approaches. This work reports a facile synthetic method to synthesize a large family of pyrazole molecule‐protected borates in a rapid and precise manner under mild conditions. A unique cyclic eight‐membered B4O4‐ring has been identified as the cluster core for all these hybrid borates with two different conformations (boat and crown). This strategy can be applied to a system of pyrazolyl molecules to generate such hybrid borates in two independent routes from organoboronic or inorganic boric acids. Furtherly, the mechanism of ‘click reaction’ between boric acid and pyrazole induced by copper ions has been proposed based on the synthetic conditions and the structure of intermediate. Due to the bimetallic Cu sites and the functional surfaces, these materials can be used as electrocatalysts for CO2 reduction reaction and efficiently enhance the selectivity of HCOOH and C2H4. Our strategy can be regarded as a typical template technique for organic molecule‐protected borates.

CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere

AbstractHomogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO2 reduction. Primary coordination sphere of metal complexes plays a key role in regulating its intrinsic redox properties and catalytic activity. However, the overall reduction efficiency of CO2 is also bound up with the substrate activation process. Transition‐metal complexes are hoped to exhibit reasonable redox potential, reactive activity, and stability, while binding and activating CO2 molecules to achieve efficient CO2 reduction. Construction of second coordination sphere, especially hydrogen‐bonding network of transition‐metal complexes, is reported to be the “kill two birds with one stone” strategy to realize efficient CO2 reduction catalysis via systematic catalyst properties modulation and substrate activation. Herein, we present recent progress on the construction of hydrogen‐bonding network in the second coordination sphere of metal complexes by ligand modification or the introduction of exogenous organic ligand, and the resulted productive enhancement of the catalytic performance of metal complexes by the improvement of adsorption capacity and activation of CO2, proton transfer rate, and stability of reaction intermediates, and so forth.

DFT analysis of the concerted metalation-deprotonation in earth-abundant 3d-transition-metal mediated C–H activations

Methane activation and functionalization under catalytic conditions remains a challenge that must be addressed to make this abundant alkane, the primary component of natural gas, into a more useful resource. One possible method of methane activation is concerted metalation-deprotonation (CMD), which thus far has been largely limited to precious metals and more reactive substrates. In this DFT study, CMD activation of methane is assessed employing more earth-abundant 3d transition metal complexes to assess the effects of metal, ligands, etc. upon the kinetics and thermodynamics of methane C–H activation via CMD mechanisms. Key findings from this study reveal the strong influence spin states as well as ligand modification have on the activation energy barriers. Moreover, an unexpected observation pertaining to ligand modification was seen where the acetate ligand exhibited higher computed free energy barriers compared to the trifluoroacetate ligand. Although acetate is more basic than trifluoroacetate, the ligand directing effects ultimately had a greater influence on the thermodynamic control of the CMD mechanism being studied here.

Engineering supramolecular peptide nanofibers for in vivo platelet-hitchhiking beyond ligand-receptor recognition.

Ex vivo or in vivo cell-hitchhiking has emerged as a potential means for efficient drug delivery and various disease therapies. However, many challenges remain, such as the complicated engineering process and dependence on ligand-receptor interaction. Here, we present a simple in vivo platelet-hitchhiking strategy based on self-assembling peptides without ligand modification. The engineered peptide nanofibers can hitchhike ultrafast (<5 s) and efficiently on both resting and activated platelets in a receptor-independent and species-independent manner. Mechanistic studies showed that unique secondary structure of nanofibers, which lead to surface exposure of hydrophobic and hydrogen bond-forming groups, might primarily contribute to the selective and efficient platelet-hitchhiking behavior. After intravenous injection, these peptide nanofibers hitchhiked in situ on circulating platelets and achieved almost 20-fold lung accumulation. Our study provides not only a different paradigm of in vivo platelet-hitchhiking beyond ligand-receptor recognition but also a potential strategy for lung-targeted drug delivery and pulmonary disease therapy.

From [2Mn2S] Diamond Cores to Butterfly Rhombs: Transformations That Highlight Alternating Peptide Binding Sites.

Thiocarboxamide chelates are known to assemble [2Mn2S] diamond core complexes via μ-S bridges that connect two MnI(CO)3 fragments. These can exist as syn- and anti-isomers and interconvert via 16-electron, monomeric intermediates. Herein, we demonstrate that reduction of such Mn2 derivatives leads to a loss of one thiocarboxamide ligand and a switch of ligand binding mode from an O- to N-donor of the amide group, yielding a dianionic butterfly rhomb with a short Mn0-Mn0 distance, 2.52 Å. Structural and chemical analyses suggest that reduction of the Mn(I) centers is dependent on the protonation state of the amide-H, as total deprotonation followed by reduction does not result in the reduction of the Mn2 core. Partial deprotonation followed by reduction suggests a pathway that involves monomeric Mn(CO)3(S-O) and Mn(CO)3(S-N) intermediates. Ligand modifications to tertiary amides that remove the possibility of amide-H reduction led to complexes that preserve the [2Mn2S] diamond core during chemical reduction. Further comparison with the tethered system, linking the Mn(CO)3(S-O) sites together, suggests that dimer dissociation is necessary for the overall reductive transformation. These results highlight organomanganese carbonyl chemistry to establish illustrations of peptide fragment binding modes in the uptake of low-valent metal carbonyls related to binuclear active sites of biocatalysts.

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis.

The development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand-modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand-modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure-performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Structural and theoretical insights into the influence of thiocyanate ligands on divalent metal complexes with terpyridine derivatives

Four complexes with terpyridine derivative, thiocyanate anion, and selected d-electron metals were studied. The obtained complexes of the formulation [M(ftpy)(SCN)2(CH3OH)]•DMF (M = Mn (1), Co (2), Ni (3)) and [Cu(ftpy)(NCS)2]•H2O (4), where ftpy = 4′‐(furan-2-yl)-2,2′:6′,2′′‐terpyridine, were characterized using FTIR and UV–Vis spectroscopies, magnetic studies, elemental analysis, and single crystal X-ray crystallography. All compounds crystallize in a triclinic crystal system with space group P1¯ and 1–3 are isomorphous and isostructural. The effect of the modification of the terpyridine ligand and the presence of the thiocyanate ligand on the structure has been verified. Interesting dependence was found in the structure of compound 4, where the two thiocyanate ligands are differently coordinated, one via N and the other via S, and the formation of complex dimers connected through hydrogen bonds is observed. The π-stacking interactions and the resulting solid-state architectures of compounds 1–4 were inspected through a combination of DFT calculations, QTAIM, and NCIPlot analyses, and the stability of the complexes was studied by UV–Vis spectroscopy in various solvents.

Orientational Compatibility Modulation of Ligands in Low-Symmetry Multi-Cavity Discrete Coordination Cages by Neighbouring Cage Participation.

Complexation of Pd(II) with a designer unsymmetrical bis-monodentate ligand (2:4 ratio) yielded a specific Pd2L4 type "single-cavity discrete coordination cage" (SCDCC), from a pool of 4 isomeric structures. The observed selctivity is attributed to inherent orientational preference of the ligand strands around the metal centers. Crafting a short coordinating arm at either ends of the bis-monodentate ligand (i.e the longer-arm) produced a pair of unsymmetrical isomeric tris-monodentate ligands; whereas crafting the same short-arm at both ends of the ligand gives an unsymmetrical tetrakis-monodentate ligand. Complexation of Pd(II) with either of the isomeric tris-monodenate ligands (3:4 ratio) resulted in corresponding low-symmetry "multi-cavity discrete coordination cage" MCDCC having two conjoined cavities, though the inherent relative orientational preference of the longer arms is not achievable in these cages. The enforced orientation is sustained by "Neighbouring Cage Participation" (NCP). However, one-pot combination of Pd(II), with a mixture of isomeric tris-monodenate ligands in 3:2:2 ratio produced an integratively self-sorted mixed-ligated MCDCC from a pool of 31 structures. Also, mixing Pd(II) with the tetrakis-monodentate ligand produced a MCDCC having three conjoined cavities. The inherent orientational preference of longer-arm of the ligand strands is retained in the mixed-ligated double-cavity and the homo-ligated triple cavity cages.

Orientational Compatibility Modulation of Ligands in Low‐Symmetry Multi‐Cavity Discrete Coordination Cages by Neighbouring Cage Participation

Complexation of Pd(II) with a designer unsymmetrical bis‐monodentate ligand (2:4 ratio) yielded a specific Pd2L4 type “single‐cavity discrete coordination cage” (SCDCC), from a pool of 4 isomeric structures. The observed selctivity is attributed to inherent orientational preference of the ligand strands around the metal centers. Crafting a short coordinating arm at either ends of the bis‐monodentate ligand (i.e the longer‐arm) produced a pair of unsymmetrical isomeric tris‐monodentate ligands; whereas crafting the same short‐arm at both ends of the ligand gives an unsymmetrical tetrakis‐monodentate ligand. Complexation of Pd(II) with either of the isomeric tris‐monodenate ligands (3:4 ratio) resulted in corresponding low‐symmetry “multi‐cavity discrete coordination cage” MCDCC having two conjoined cavities, though the inherent relative orientational preference of the longer arms is not achievable in these cages. The enforced orientation is sustained by “Neighbouring Cage Participation” (NCP). However, one‐pot combination of Pd(II), with a mixture of isomeric tris‐monodenate ligands in 3:2:2 ratio produced an integratively self‐sorted mixed‐ligated MCDCC from a pool of 31 structures. Also, mixing Pd(II) with the tetrakis‐monodentate ligand produced a MCDCC having three conjoined cavities. The inherent orientational preference of longer‐arm of the ligand strands is retained in the mixed‐ligated double‐cavity and the homo‐ligated triple cavity cages.

Boosting electrocatalytic oxygen reduction of Fe-Co polyphthalocyanine via the synergy of metal component optimization and axial ligand modification

Conjugated metal polyphthalocyanine (MPPc) organic skeletons, a kind of novel porous materials containing inherent M−N4 highly active sites, are of great significance for oxygen reduction reaction (ORR). Herein, bimetallic Fe-Co phthalocyanine covalent polymers (denoted as FeCoPPc) were prepared as ORR electrocatalysts through a solvothermal process and subsequent oxidation treatment. Meanwhile, the effect of axial oxygen-containing ligands of metal centers on the catalytic kinetic processes was also investigated. Benefiting from the highly exposed bimetal active sites and the finely designed ligand structure, FeCoPPc with optimized Fe/Co ratio and ClO3− coordination (Fe0.9Co0.1PPc-ClO3) displayed an outstanding ORR electrocatalytic activity and superior durability compared to 20 % Pt/C, manifested by an onset potential of 0.986 V vs. reversible hydrogen electrode (RHE) and a half-wave potential of 0.923 V vs. RHE in a 0.1 M KOH solution. This work may guide the rational design of high-performance electrocatalysts to regulate the catalytic activity.

Photoredox Oxidation of Alkanes by Monometallic Copper-Oxygen Complexes Using Visible Light Including One Sun Illumination.

Oxygenation of hydrocarbons offers versatile catalytic routes to more valuable compounds, such as alcohols, aldehydes, and ketones. Despite the importance of monometallic copper-oxygen species as hydroxylating agents in biology, few synthetic model compounds are known to react with hydrocarbons, owing to high C-H bond dissociation energies. To overcome this challenge, the photoredox chemistry of monometallic copper (pyrazolyl)borate complexes coordinated by chlorate has been explored in the presence of C1-C6 alkanes with BDEs ≥ 93 kcal/mol. Ethane is photooxidized at room temperature under N2 with yields of 15-30%, which increases to 77% for the most oxidizing tris(3,5-trifluoromethyl-pyrazolyl)borate complex (Cu-3). This complex also promotes the photooxidation of methane to methanol in significant yield (38%) when the photoredox reaction is run under aerobic conditions. Ligand modification alters the reaction selectivity by tuning the redox potential. The ability to activate 1° C-H bonds of C1-C6 alkanes using visible light is consistent with the photogeneration of a powerfully oxidizing copper-oxyl, which is supported by photocrystallographic studies of the tris(3,4,5-tribromopyrazolyl)borate chlorate complex. Mechanistic studies are consistent with the hydrogen atom abstraction of the C-H bond by the copper-oxyl intermediate. We demonstrate for Cu-3 with hexane as an exemplar, that the photoredox chemistry may be achieved under solar conditions of one-sun illumination.

Organometallic Iridium-Complex-Functionalized Nanographene Catalysts for Low-Temperature Hydrogenation of Carbonyl Derivatives.

An organometallic iridium (Ir)-complex-functionalized nanographene catalyst Ir-PyPh-GC was prepared via a two-step strategy involving amide ligand modification and metal Ir coordination. Ir-PyPh-GC showed ultrahigh hydrogenation capability, good recyclability, and selectivity for carbonyl derivatives (ketones, aldehydes, and quinones) at a low temperature (40 °C). The as-prepared Ir-complex-based catalyst is less expensive, making it feasible for industrial application.

Synergistic surface ligand modification of Ni-Pt bimetallic nanozymes: Enhanced catalytic activity and versatile detection of penicillin

Monitoring and control of penicillin (PCN) in the environment are critically important for reducing the emergence and dissemination of antibiotic-resistant bacteria, ensuring food safety, and safeguarding human health. In this study, we introduce a novel and facile strategy for modulating the catalytic activity of bimetallic nanozymes through surface ligand engineering. Experimental activity assays and theoretical model calculations confirm that Ni-Pt nanozymes coated with polyallylamine hydrochloride (PAM) exhibit significantly enhanced peroxidase (POD)-like activity compared to their counterparts coated with conventional polyvinyl pyrrolidone (PVP) and polystyrene sulfonate (PSS). Leveraging the potent reactivity between PCN and the hydroxyl radicals (∙OH) generated by Ni-Pt@PAM catalytic system, we have developed a colorimetric sensor that directly detects PCN, demonstrating a linear response range from 0.5 to 10 μM and detection limit as low as 13.5 nM. Additionally, a fluorescent sensing platform utilizing self-synthesized fluorophore Rho-Si based on inner filter effect (IFE), has been successfully established. These two sensing platforms, capable of generating both colorimetric and fluorescent signals, enable sensitive, rapid, and straightforward detection of PCN in water samples. This work not only offers an innovative approach for tuning the POD-like activity of Ni-Pt bimetallic nanozymes but also presents a promising avenue for their application in PCN monitoring.

Surfactant-Free Method to Prevent Gold Nanoparticle Aggregation and Its Surface-Enhanced Raman Scattering Applications.

The introduction of surfactants to stabilize colloidal citrate-reduced gold nanoparticles (prevent aggregation) is usually used in surface-enhanced Raman scattering (SERS) applications. However, the surfactants have many drawbacks for SERS applications, such as increasing the SERS background and blocking surface active sites. Here, we develop a surfactant-free method to stabilize colloidal cit-AuNPs based on alkali regulation, and this method can prevent gold nanoparticle aggregation under different harsh treatments, including ligand modification, centrifugation-based washing/enrichment, and salt addition. The SERS spectra, density functional theory simulation, and ζ potentials of cit-AuNPs indicate that the stability of enhanced cit-AuNPs under alkaline conditions is attributed to both the increased negative charge density (by ∼6 times from pH 7 to 12) and the molecular configuration on the metal surface. Compared with surfactant-based methods, this method can well maintain the inherent optical and interface properties of nanoparticles, avoid the SERS background, and avoid blocking of the surface active site due to the presence of surfactants. This method will enable AuNPs to have a wide range of applications in areas such as highly sensitive SERS sensors.

Precise customization of plant architecture by combinatorial genetic modification of peptide ligands

Precise customization of plant architecture by combinatorial genetic modification of peptide ligands

Surface Modification of Gold Nanorods: Multifunctional Strategies and Application Prospects.

Gold nanorods (AuNRs), as an important type of gold nanomaterials, have attracted much attention in the nano field. Compared with gold nanoparticls, AuNRs have broader application potential due to their tunable localized surface plasmon resonance properties and anisotropic shapes. Yet, conventional synthesis methods using surfactants have limited the use of AuNRs in a variety of fields such as biomedical applications, plasma-enhanced fluorescence, optics and optoelectronic devices. To solve this problem and improve the stability and biocompatibility of AuNRs, researchers in recent years have used surface modification and functionalization to modify AuNRs, among which the introduction of organic ligands to prepare organic/gold hybrid nanorods has become an effective strategy. Organic materials have better toughness and easy processing, and by introducing organic ligands into the surface of AuNRs, the molecular-level composite of organic and inorganic materials can be realized, thus obtaining hybrid nanorods with excellent properties. This paper reviews the research progress of hybrid nanocomposites, and introduces the synthesis methods of AuNRs and the development of surface ligand modification, then summaries the applications of a wide variety of ligands. Also, the advantages and disadvantages of different ligands and their roles in further self-assembly processes are discussed.

DFT Study on the Second-Order NLO Responses of 2-Phenyl Benzoquinoline Ir(III) Complexes by Substituents and Redox Effects.

Metal complexes have received extensive attention in nonlinear optical (NLO) materials because of their advantages, such as shorter response times and more flexible structural properties. Density functional theory is used in investigating the geometric structures, electronic structures, charge centroid, and first hyperpolarizability (βtot) of a series of selected 15 coordinated Ir(III) complexes. The substitute effect and one-electron redox process effects on the structures and properties of 15 coordinated Ir(III) complexes are considered. When the electron-withdrawing group is introduced into the ligand, the HOMO-LUMO energy gap decreases and the βtot value increases, positively correlating with the electron-withdrawing ability. The single electron redox process can also improve the NLO responses of complexes, especially the reduction process. The βtot value of complex 4- is the largest, 2078 times higher than that of complex 4. The analysis shows that the variation of NLO responses of complexes is ascribed to the change of electronic structures and the charge transfer modes induced by the ligand modification and redox process, which are considered to be two effective methods in enhancing the NLO responses of 2-phenyl benzoquinoline Ir(III) complexes. This study aims to offer design insights into high-performance nonlinear optical materials.

Exploration of the tunability of BRD4 degradation by DCAF16 trans-labelling covalent glues

Chemically induced proximity modalities such as targeted protein degradation (TPD) hold promise for expanding the number of proteins that can be manipulated pharmacologically. However, current TPD strategies are often limited to proteins with preexisting ligands. Molecular glues (e.g. glutarimide ligands for CUL4CRBN), offer the potential to target undruggable proteins. Yet, their rational design is largely unattainable due to the unpredictability of the ‘gain-of-function’ nature of the glue interaction upon chemical modification of ligands. We recently reported a covalent trans-labelling glue mechanism which we named ‘Template-assisted covalent modification’, where an electrophile decorated BRD4 inhibitor was effectively delivered to a cysteine residue on DCAF16 due to an electrophile-induced BRD4-DCAF16 interaction. Herein, we report our efforts to evaluate how various electrophilic modifications to the BRD4 binder, JQ1, affect DCAF16 recruitment and subsequent BRD4 degradation efficiency. We discovered a moderate correlation between the electrophile-induced BRD4-DCAF16 ternary complex formation and BRD4 degradation. Moreover, we show that a more solvent-exposed warhead presentation optimally recruits DCAF16 and promotes BRD4 degradation. The diversity of covalent attachments in this class of BRD4 degraders suggests a high tolerance and tunability for the BRD4-DCAF16 interaction. This offers a new avenue for rational glue design by introducing covalent warheads to known binders.