Capping Ligands Research Articles

Bromopropane as a novel bromine precursor for the completely amine free colloidal synthesis of ultrastable and highly luminescent green-emitting cesium lead bromide (CsPbBr3) perovskite nanocrystals.

Recently, lead halide perovskite nanocrystals (PNCs) have attracted intense interest as promising active materials for optoelectronic devices. However, their extensive applications are still hampered by poor stability under ambient conditions. Oleic acid and oleylamine are the most commonly used ligands in colloidal CsPbX3 (X = Cl, Br, and I) synthesis. Oleylamine plays a dual role as it stabilizes the surface but in the long run or post-synthesis, it may disturb the colloidal stability due to facile proton exchange leading to the formation of labile oleylammonium halide, which detaches the halide ions from the NC surface. To address these issues, herein, we report an open-atmospheric, facile, efficient, and completely amine-free synthesis of cesium lead bromide perovskite nanocrystals using a novel bromine precursor, bromopropane, which is inexpensive and available at hand. The reaction mechanism follows a trioctylphosphine/oleic acid-mediated surface passivation route that provides an amine-free reaction environment to stabilize ligand capping on the NC surface. Uniform, highly monodisperse NCs of size ∼29 nm were obtained. The as-synthesized NCs have a high photoluminescence quantum yield (PLQY) of around 80%, and especially, exhibited strong stability under ambient conditions and continuous UV irradiation. The PLQY can maintain 83% of the initial one even after 120 days. Furthermore, after 96 h of continuous irradiation under UV light at 365 nm (8 W cm-2) under open ambient conditions, the photoluminescence (PL) intensity showed retention of 68% of its original value with no significant changes in the full width at half-maximum, whereas the amine-based sample retains only 5% of its original PL intensity. Furthermore, we have utilized these NCs to fabricate stable down-converted LED devices. The present work demonstrated the synthesis of ultra-stable CsPbBr3 NCs that can be an ideal candidate for display applications.

Absorption and emission in the visible range by ultra-small PbS quantum dots in the strong quantum confinement regime with S-terminated surfaces capped with diphenylphosphine

The synthesis and characterization of PbS QDs absorbing and emitting in the visible range is a very challenging task, since it requires the QDs to be within the strong quantum confinement regime (QD size<2.5 nm). It implies not only having “small” QDs, but also stable and monodisperse; characteristics that have been elusive to achieve for many researchers. In the current work, ultra-small PbS QDs (size ~2 nm) were synthesized based on a modification of the Hines method, controlling the reaction time, and adding diphenylphosphine (DPP) which serves as a catalyst and a protective agent in the reaction synthesis. Novel ultra-small PbS QDs with S-terminated surfaces were obtained, which formed at the early stages of the synthesis reaction and are stabilized by the DPP; as it was suggested by the TEM, FTIR and Raman results. The ultra-small PbS QDs display a maximum peak of optical absorption at ~532 nm, with a corresponding optical band gap of 1.82 eV; a maximum peak of emission at ~679 nm, which results in a Stokes shift of 119 nm, smaller than the Stokes shift observed in “larger” PbS QDs. These ultra-small QDs displayed an average size of ~2 nm, with a standard deviation of ~0.3 nm, which was the smallest among the synthesized samples, based on TEM measurements. Finally, the LUMO and HOMO levels were measured by means of cyclic voltammetry and optical absorption spectroscopy. The values of the optical band gap and the energies measured for the LUMO and HOMO levels of these ultra-small PbS QDs were affected by their atomistic surface arrangement and the capping ligand interacting with their surface. Producing variations in their values that doesn’t follow the trends established for quantum confinement effects related to size variation only. Thorough physical and chemical characterization of such ultra-small PbS QDs are crucial in understanding the origin of their optoelectronic properties, which will contribute to better delineate possible future applications.

Aqueous synthesis of highly luminescent ternary alloyed Mn-doped ZnSeS quantum dots capped with 2-mercaptopropionic acid

Highly photoluminescent and water dispersible ternary alloyed Mn-doped ZnSeS and core/shell Mn:ZnSeS/ZnS quantum dots (QDs) with pure dopant emission were synthesized through a simple aqueous route using thiolactic acid (2-MPA) as a capping ligand. Transmission electron microscopy and X-ray diffraction show that Mn:ZnSeS nanocrystals are of spherical shape, with a diameter of 2.4 nm and a cubic zinc blende structure. With the overcoating of the ZnS shell, the particle size increases to 3.7 nm, which confirms the epitaxial growth of the shell on Mn:ZnSeS cores. The photoluminescence (PL) quantum yield depends on the Mn loading and reaches 22% for Mn:ZnSeS cores doped with 10% Mn and 41% after the growth of ZnS at the surface of the cores due to the effective elimination of surface-trap states. Mn:ZnSeS QDs exhibit also long PL lifetimes (up to 681 μs) indicating that the emission originates from the spin forbidden Mn2+ 4T1 → 6A1 transition. Electron paramagnetic resonance and X-ray photoelectron spectroscopy results suggest that Mn2+ ions are located at the interface of core/shell Mn:ZnSeS/ZnS QDs. Further, the stability of Mn:ZnSeS/ZnS QDs was also investigated along with their transfer in organic phase using octanethiol.

Photoluminescence Investigation of Carrier Localization in Colloidal PbS and PbS/MnS Quantum Dots.

The existence of surface organic capping ligands on quantum dots (QDs) has limited the potential in QDs emission properties and energy band gap structure alteration as well as the carrier localization. This drawback can be addressed via depositing a thin layer of a semiconductor material on the surface of QDs. Herein, we report on the comparative study for photoluminescent (PL) properties of PbS and PbS/MnS QDs. The carrier localization effect due to the alteration of energy band gap structure and carrier recombination mechanism in the QDs were investigated via PL measurements in a temperature range of 10–300 K with the variation of the excitation power from 10 to 200 mW. For PbS QDs, the gradient of integrated PL intensity (IPL) as a function of excitation power density graph was less than unity. When the MnS shell layer was deposited onto the PbS core, the PL emission exhibited a blue shift, showing dominant carrier recombination. It was also found that the full width half-maximum showed a gradual broadening with the increasing temperature, affirming the electron–phonon interaction.

Quantitative Analysis of DNA-Mediated Formation of Metal Nanocrystals.

The predictive synthesis of metal nanocrystals with desired structures relies on the precise control of the crystal formation process. Using a capping ligand is an effective method to affect the reduction of metal ions and the formation of nanocrystals. However, predictively synthesizing nanostructures has been difficult to achieve using conventional capping ligands. DNA, as a class of the promising biomolecular capping ligands, has been used to generate sequence-specific morphologies in various metal nanocrystals. However, mechanistic insight into the DNA-mediated nanocrystal formation remains elusive due to the lack of quantitative experimental evidence. Herein, we quantitatively analyzed the precise control of DNA over Ag+ reduction and the structures of resulting Au-Ag core-shell nanocrystals. We derived the equilibrium binding constants between DNA and Ag+, the kinetic rate constants of sequence-specific Ag+ reduction pathways, and the percentage of active surface sites remaining on the nanocrystals after DNA passivation. These three synergistic factors influence the nucleation and growth process both thermodynamically and kinetically, which contributed to the morphological evolution of Au-Ag nanocrystals synthesized with different DNA sequences. This study demonstrates the potential of using functional DNA sequences as a versatile and tunable capping ligand system for the predictable synthesis of metal nanostructures.

Direct Observation of Shallow Trap States in Thermal Equilibrium with Band‐Edge Excitons in Strongly Confined CsPbBr3 Perovskite Nanoplatelets

AbstractLead halide perovskites exhibit great potential for light‐emitting devices. Enhanced photoluminescence (PL) is obtained in perovskite materials of reduced dimensionalities due to the large exciton binding energy. However, as the nanocrystal size is reduced, the surface‐to‐volume ratio increases, leading to an abundance of surface defects. Here, a fast PL decay, 3–10 ps, is observed in quasi‐1D CsPbBr3 perovskite nanoplatelets using broadband fluorescence upconversion spectroscopy. This decay is attributed to reversible trapping of band‐edge excitons into dark states that lie close to the band edge. A simplified model is proposed to further confirm the presence of shallow traps and to fit the data obtained by ultrafast spectroscopy for multiple samples. Finally, the presence of deep trap states in aged nanoplatelets is revealed, likely arising from desorption of the organic capping ligands from the surface. Exciton trapping into these states is slower, 20–30 ps, but leads to a decrease in the photoluminescence quantum yield. These results may not only explain the extended luminescence lifetimes that have been reported for perovskite nanocrystals but also demonstrate the potential of combining ultrafast transient absorption and fluorescence up‐conversion to obtain a full description of the spectroscopic properties of the material.

A novel quinoxalinedione-bicapped tri-ruthenium carbonyl cluster [Ru3(μ-H)2(CO)6(μ3-HDCQX)2]: synthesis, characterization, anticancer activity and theoretical investigation of Ru–Ru and Ru–Ligand bonding interactions

A new tri-ruthenium dihydrido cluster, [Ru3(μ-H)2(CO)6(HDCQX)2] (1), in which two HDCQX (H2DCQX = 6,7-dichloroquinoxaline-2,3-dione) ligands cap both faces of the tri-ruthenium triangle similarly through oxygen atoms, has been synthesized and characterized by mass, IR, NMR (1H and 13C) and electronic spectroscopy. DFT calculations, in both gas and solution (CPCM/DMSO) phases, were performed to analyze the electronic structure of the cluster and interpret its vibrational and NMR spectra. The presence of non-equivalent bridging hydrides was assigned by 1H NMR as two singlet resonances at δ −16.85 and −17.67 ppm and confirmed by theoretical DFT-GIAO calculations at δ −12.92 and −14.48 ppm. Time-dependent density functional theory (TD-DFT) calculations, performed to characterize the frontier orbitals and interpret the electronic spectrum, indicated that the lowest-energy transition of 1 originates from a highly delocalized HOMO with Ru–Ru (σ), Ru–CO (π) and Ru–CO (σ*) contributions and ends in the LUMO with Ru1–Ru2–Ru3 (σ*) and QX/QX′ (π*) anti-bonding character. The natural transition orbital (NTO) corresponding to this transition revealed a decrease of the electron density on the Ru1Ru2(CO)4 fragment and an increase of the electron density on the Ru1–Ru2–Ru3 unit and the HDCQX ligands. The Ru–Ru and Ru–ligand bonding was studied by the quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF) methods. Both confirmed the presence of unique bonding between the Ru1 and Ru2 atoms and not between Ru3 and the other Ru atoms. While the QTAIM assigned the Ru1–Ru2 bonding as a transit between pure closed-shell and pure shared-shell interactions, the ELF analysis suggested that this bond is dominated by a fluctuation of electron density. The covariance analysis indicated that the core basin populations C(Ru1) and C(Ru2) account for 76% of the V(Ru1, Ru2) variance. Natural bond orbital (NBO) analysis of the Ru3(µ-H)2O4(CO)6 unit indicated a 2c–2e bonding type for the Ru–O, Ru–C and Ru–Ru bonds with orbital occupations of 1.88–1.95, 1.95–1.96, and 1.57 e, respectively, and a 3c–2e bonding for the Ru–H–Ru bonds with an orbital occupation of ca. 1.7 e. NBO second-order perturbative energy analysis was performed to estimate the strength of the Ru–CO π-back-donation and to establish a correlation between the stabilization energy (E(2)) and the spectroscopic data. Although the calculated stabilization energy (E(2)total) follows the expected trend of decreasing the CO stretching frequency (νCO) and increasing the 13CO chemical shift with the extent of the Ru–CO π-back-donation, the latter parameter was more consistent in estimating the strength of such interactions. The in vitro anticancer activities of the title compound and cisplatin were determined against three common types of human cancer cell lines, HCT-116 (colon), HELA (cervix) and MCF-7 (breast). The IC50 values of 3.18 ± 0.40, 4.21 ± 0.29 and 5.39 ± 0.52 μM, respectively, represent 4- and 2-times improvement in potency relative to cisplatin (12.06 ± 1.28, 10.34 ± 2.08 and 6.29 ± 1.68 μM, respectively) against the HCT-116 and HeLa cancer cell lines.

Antioxidative Stannous Oxalate Derived Lead-Free Stable CsSnX3 (X=Cl, Br, and I) Perovskite Nanocrystals.

Lead-free CsSnX3 perovskite NCs are becoming a promising alternative to CsPbX3 (X=Cl, Br, I), but suffer from extremely poor stability. Herein, we highlight the significant effect of SnII precursors used in the synthesis on the stability of the resultant CsSnX3 NCs. A method is proposed for synthesizing CsSnX3 NCs using Cs2 CO3 , SnC2 O4 , and NH4 X as corresponding constituent precursors, wherein the ratio of reactants can be easily adjusted. Stable CsSnX3 NCs can be obtained with the use of antioxidative SnC2 O4 as the SnII precursor. Experimental results show that the improvement of NCs stability is mainly ascribed to the role of oxalate in the SnC2 O4 precursor. Oxalate ion has a strong antioxidative ability and can effectively inhibit the oxidation of SnII during the synthesis. Besides, oxalate as a bidentate capping ligand is shown to be coordinated on the surface of formed NCs. This can not only passivate the uncoordinated Sn on the surface but also prevent the oxidation of the NCs.

Antioxidative Stannous Oxalate Derived Lead‐Free Stable CsSnX3 (X=Cl, Br, and I) Perovskite Nanocrystals

AbstractLead‐free CsSnX3 perovskite NCs are becoming a promising alternative to CsPbX3 (X=Cl, Br, I), but suffer from extremely poor stability. Herein, we highlight the significant effect of SnII precursors used in the synthesis on the stability of the resultant CsSnX3 NCs. A method is proposed for synthesizing CsSnX3 NCs using Cs2CO3, SnC2O4, and NH4X as corresponding constituent precursors, wherein the ratio of reactants can be easily adjusted. Stable CsSnX3 NCs can be obtained with the use of antioxidative SnC2O4 as the SnII precursor. Experimental results show that the improvement of NCs stability is mainly ascribed to the role of oxalate in the SnC2O4 precursor. Oxalate ion has a strong antioxidative ability and can effectively inhibit the oxidation of SnII during the synthesis. Besides, oxalate as a bidentate capping ligand is shown to be coordinated on the surface of formed NCs. This can not only passivate the uncoordinated Sn on the surface but also prevent the oxidation of the NCs.

A sandwich-type cluster containing Ge@Pd3 planar fragment flanked by aromatic nonagermanide caps

Sandwich-type clusters with the planar fragment containing a heterometallic sheet have remained elusive. In this work, we introduce the [K(2,2,2-crypt)]4{(Ge9)2[η6-Ge(PdPPh3)3]} complex that contains a heterometallic sandwich fragment. The title compound is structurally characterized by means of single-crystal X-ray diffraction, which reveals the presence of an unusual heteroatomic metal planar fragment Ge@Pd3. The planar fragment contains a rare formal zerovalent germanium core and a peculiar bonding mode of sp2-Ge@(PdPPh3)3 trigonal planar structure, whereas the nonagermanide fragments act as capping ligands. The chemical bonding pattern of the planar fragment consists of three 2c-2e Pd-Ge σ-bonds attaching Pd atoms to the core Ge atom, while the binding between the planar fragment and the aromatic Ge9 ligands is provided by six 2c-2e Pd-Ge σ-bonds and two delocalized 4c-2e σ-bonds. The synthesized cluster represents a rare example of a sandwich compound with the heteroatomic metal planar fragment and inorganic aromatic capping ligands.

Probing the structure and functionalized surface of colloidal AuSe

We report on the synthesis of the less explored AuSe and investigate the influence capping agents; oleylamine (OLA), 1-dodecanethiol (IDDT), and oleic acid (OA) have on its structure and surface. TEM showed long belt-like structures for both OLA and OA-capped materials and nanorods for 1DDT-AuSe. XRD diffractograms and Raman spectra showed the presence of both α- and β-AuSe polymorphs, with the dominance of the α-phase in all three materials. The methylene stretching frequencies in the FTIR spectra confirmed capping by the organic ligands. High-resolution XPS spectra of the Au4f core level showed evidence of the Au + ions. The high total peak area percentage of the Au + ions in OLA-AuSe (90%), 1DDT (23%), and OA (21%) suggests that OLA is the best capping ligand. DFT calculations on the adsorption of the ligands on AuSe showed weak interaction on (001) plane suggesting anisotropic growth along this plane and preference for the α-phase.

Cooperativity Between Zirconium Dioxide Nanoparticles and Extreme Pressure Additives in Forming Protective Tribofilms: Toward Enabling Low Viscosity Lubricants

Realizing the efficiency benefits of low viscosity lubricants requires novel strategies to avoid failures resulting from increased boundary contact. Zirconium dioxide (ZrO2) nanoparticles (NPs) form protective tribofilms through tribosintering at lubricated contacts in pure hydrocarbon base oils, suggesting they hold promise for reducing boundary contact-induced failures. However, their tribological behavior alongside co-additives found in fully formulated oils has not been examined in depth. Here, the macroscopic tribological performance of dispersed ZrO2 NPs (1 wt% loading; 5 nm diameter nearly spherical ZrO2 tetragonal phase NPs with organic capping ligands for oil solubility) with and without the presence of co-additives found in fully formulated commercial gear oils was studied using a mini-traction machine (MTM). The results show that ZrO2 NPs reproducibly develop surface-bound ~ 100 nm thick tribofilms on both contacting surfaces under a wide range of rolling-sliding contact conditions, from 0 to 100% slide-to-roll ratio. Steady-state traction coefficient values of ZrO2 tribofilms formed alongside co-additives (0.10–0.11) do not substantially differ from ZrO2 tribofilms formed in neat polyalphaolefin base oils (0.10–0.13). However, there is improvement in the tribological performance of the contact, with at least a twofold reduction of wear of the steel. This behavior is proposed to be a result of cooperating mechanisms, where the extreme pressure additives adsorbed on the steel surfaces protect them against early adhesive wear, during the time that a protective ZrO2 tribofilm incorporating the co-additives forms on the steel surfaces, preventing further wear.

Hot Carrier Transfer-Induced Photodegradation at a Thiolated Au/TiO2 Interface under X-ray Irradiation

This work presents a mechanistic interpretation of hot carrier-driven photoreduction of Au NPs coupled with the oxidative photodegradation of thiol-containing capping ligands on Au/TiO2 catalysts u...

Spectroscopic Investigation of Interaction between the 4f Electronic System and the Photoexcited Cyclic π System in Terbium(III) Monoporphyrinato Complex.

Electronic interaction between the total angular momentum (J) of the 4f electronic system and an angular momentum (L) of the photoexcited cyclic π system in a terbium(III) monoporphyrinato complex with a capping ligand cyclen, [Tb(TPP)(cyclen)]Cl (TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4,7,10-tetraazacyclododecane), have been investigated by varied-temperature and varied-magnetic-field magnetic circular dichroism (MCD) spectroscopy. Three MCD A-term patterns which correspond to B(0,0), Q(0,0), and Q(1,0) absorption bands were observed for the complex which was incorporated into a thin film of poly(methyl methacrylate), PMMA, as well as that in solution phase. The A-term patterns in the Soret band region and Q-band region were found to show opposite behavior with changes in temperature and magnetic field. This finding clearly indicated not only the presence of the J-L interaction but also the different directions of the J-L interaction; i.e., J and L interact ferromagnetically in the Q(0,0) and Q(1,0) states, while antiferromagnetically in the B(0,0) state. The magnitude of the interaction was determined by simulation-based fitting to experimental ratios, where refers to the A-term intensity and to the oscillator strength of the band. The first ab initio study was also carried out for further insight into the interaction. From the computational study, the relationship between the orbital angular momentum of π electronic system, L(π), and the orbital angular momentum of the 4f system, L(f), was clearly revealed. A computational approach to determine the magnitude and the direction of J-L interaction was established.

Simpler and Cleaner Synthesis of Variously Capped Cobalt Nanocrystals Applied in the Semihydrogenation of Alkynes.

Unlike the classical organometallic approach, we report here a synthetic pathway requiring no reducing sources or heating to produce homogeneous hexagonal-close-packed cobalt nanocrystals (Co NCs). Involving a disproportionation process, this simple and fast (6 min) synthesis is performed at room temperature in the presence of ecofriendly fatty alcohols to passivate Co NCs. Through a recycling step, the yield of Co NCs is improved and the waste generation is limited, making this synthetic route cleaner. After an easy exchange of the capping ligands, we applied them as unsupported catalysts in the stereoselective semihydrogenation of alkynes.

Inducing Defects in 19F-Nanocrystals Provides Paramagnetic-free Relaxation Enhancement for Improved In Vivo Hotspot MRI.

Paramagnetic relaxation enhancement (PRE) is the current strategy of choice for enhancing magnetic resonance imaging (MRI) contrast and for accelerating MRI acquisition schemes. Yet, debates regarding lanthanides’ biocompatibility and PRE-effect on MRI signal quantification have raised the need for alternative strategies for relaxation enhancement. Herein, we show an approach for shortening the spin–lattice relaxation time (T1) of fluoride-based nanocrystals (NCs) that are used for in vivo 19F-MRI, by inducing crystal defects in their solid-crystal core. By utilizing a phosphate-based rather than a carboxylate-based capping ligand for the synthesis of CaF2 NCs, we were able to induce grain boundary defects in the NC lattice. The obtained defects led to a 10-fold shorter T1 of the NCs’ fluorides. Such paramagnetic-free relaxation enhancement of CaF2 NCs, gained without affecting either their size or their colloidal characteristics, improved 4-fold the obtained 19F-MRI signal-to-noise ratio, allowing their use, in vivo, with enhanced hotspot MRI sensitivity.

Modulating Charge Carrier Dynamics and Transfer via Surface Modifications in Organometallic Halide Perovskite Quantum Dots.

We investigate the effect of functionalization by acid/amine combinations of four aromatic capping ligands on the optoelectronic properties of CH3NH3PbBr3 perovskite quantum dots (PQDs). These include benzoic acid (BA), phenylacetic acid (PAA), benzylamine, and isopropyl benzylamine. We observe that charge transfer efficiency in PQD films comprising BA-ligated samples varies between 12% and 95% as the dot density is tuned from 102 to 105 dots/μm2 but is consistently ∼92% over that entire range for PAA-ligated PQDs. As temperature T decreases, initially, recombination is dominated by bound or trapped excitons, but below 80 K, spectral broadening, accompanied by free excitonic behavior, is observed. Our results indicate enhanced charge delocalization at lower values of T, which reduces the level of exciton confinement and recombination decay rates and underlines the importance of investigating PQD-ligand interactions at a fundamental level given the significant effect minute changes in ligand structures have on the optoelectronic properties of quantum dots.

Ultrashort peptide-stabilized copper nanoclusters with aggregation-induced emission

Here, we report a facile, one-pot strategy for the fabrication of copper nanoclusters (CuNCs) with orange-red fluorescent emission in the presence of an ultrashort peptide, I3R, and GSH. The effects of the reaction temperature, pH value, GSH and I3R concentrations on the fluorescence properties of I3R-GSH-CuNCs were investigated in detail. By forming compact and ordered self-assembled microstructures, such as nanofibers and helical nanofibers, the as-prepared I3R-GSH-CuNCs exhibit an aggregation-induced emission enhancement effect. Due to the coordination interaction between the Cu core and the capping ligands, which facilitates ligand-to-metal charge transfer (LMCT), the photoluminescence lifetime of I3R-GSH-CuNCs can be prolonged to 19.3 μs. The CD spectra of samples with helical nanofibers exhibit a negative band in the range of 300 ∼ 320 nm, indicating that the CuNCs obtained in this work are chiral, and their chirality was induced by the chiral ligands GSH and I3R. A possible mechanism of the self-assembly-induced emission enhancement is proposed. Furthermore, stable CuNCs were used to fabricate prototype down conversion LEDs with orange emission.

Paramagnetic properties of manganese chelated on glutathione-exfoliated MoS2

Generation of zero-dimensional molybdenum disulphide (MoS2) nanoparticles with effective chemical and physical properties have offered a widerange of applications. The advancement in two-dimensional (2D) MoS2 functionalization materials for the fabrication of biomedical applications has become a recent trend owing to their physicochemical properties such as high surface area, mechanical properties, and excellent electrical conductivity. In this study, the pristine bulk MoS2 was exfoliated by probe sonication with glutathione (GSH) as a capping ligand to form MoS2-GSH nanoparticles. Further, the as-prepared MoS2-GSH was coated with amino terminated ethyl polyethylene glycol (MoS2-GSH-AEPEG) through electrostatic interactions between GSH and AEPEG. Thereafter, both MoS2-GSH and MoS2-GSH-AEPEG nanoparticles (NPs) were chelated with manganese (Mn) metal ion to form magnetic MoS2-GSH-Mn and MoS2-GSH-AEPEG-Mn NPs. The obtained MoS2-GSH-Mn and MoS2-GSH-AEPEG-Mn nanoparticles exhibited a spherical in shape with sizes of 60.7 and 80.6 nm, respectively. The chelated Mn2+ in the prepared MoS2 NPs was confirmed by XPS and Raman spectroscopy. The paramagnetic properties of the MoS2-GSH-Mn and MoS2-GSH-AEPEG-Mn samples were investigated using a superconducting quantum interference device at 5 K temperature and the saturation magnetization was calculated to be 17.5 and 15 emu/g for MoS2-GSH-Mn and MoS2-GSH-AEPEG-Mn, respectively. The MoS2-GSH-Mn exhibited higher magnetic hysteresis loops than MoS2-GSH-AEPEG-Mn due to shielding effects of nonmagnetic nature of PEG coating.

Steric Effect of a Capping Ligand on the Formation of Supramolecular Coordination Networks of Ni(II): Solid-State Entrapment of Cyclic Water Dimer.

Supramolecular dimer of water is the simplest of the small water clusters [(H2O)n, n = 2–10]. During the course of our work on supramolecular coordination networks of three-component systems (divalent metal ion, tridentate capping ligand, and ditopic carboxylate linker), a cyclic water dimer is found to be entrapped in the network of [Ni2(6-Mebpta)2(adc)2]·2H2O (1) (6-Mebpta = 2-methyl-N-((6-methylpyridin-2-yl)methyl)-N-(pyridin-2-ylmethyl)propan-2-amine and adc = acetylenedicarboxylate). Based on the single-crystal structure of 1, the water dimer plays an important role in connecting the bis(adc) bridged dinickel synthons to form a one-dimensional (1D) supramolecular network. To emphasize the role of 6-Mebpta in the judicious choice of components for 1, one simple modification to it by having another methyl group in the second pendant pyridyl group to make 6,6′-Me2bpta (2-methyl-N,N-bis((6-methylpyridin-2-yl)methyl)propan-2-amine) did not allow the formation of any water cluster in [Ni(6,6′-Me2bpta)(adc)(H2O)]·H2O (2), where a different coordination environment around Ni(II) is also observed. Further quantification of the difference in supramolecular interactions observed in 1 and 2 has been assessed by Hirshfeld surface analysis. Both 1 and 2 are obtained in good yields at room temperature (methanol as solvent) and are further characterized by elemental analysis, Fourier transform infrared (FTIR) and Raman spectroscopy, powder X-ray diffraction, and thermogravimetric analysis.