Ligand Exchange Procedure Research Articles

Enhancement of the alloyed CdZnSeS/ZnS quantum dots photoluminescence by thiol ligands capping

Most of the existing hydrophilization techniques for the semiconductor quantum dots (QDs) lead to degradation of photoluminescence (PL). Therefore, for the applying of QDs in the areas requiring their stability in water media (e.g. bio- and chemical analysis, labeling and sensing), it is often necessary to find a balance between high stability, good optical properties, and difficulty of acquiring. This article describes simple, fast, and easy scalable methods for alloyed CdZnSeS/ZnS QDs ligand exchange using 2-mercaptoethanol, thioglycolic, 3-mercaptorpopionic and dihydrolipoic acids. The proposed ligand exchange techniques provide the enhancement of the QDs photoluminescence intensity in contrast to most of other ligand exchange procedures on the QDs surface. In optimized conditions the twofold photoluminescence quantum yield increase compared to the initial hydrophobic CdZnSeS/ZnS QDs was achieved. Hydrophilized nanoparticles maintained colloidal stability for a period more than 13 months. The suggested mechanism of the PL increase is the passivation of the QDs surface with molecules containing a thiol group. The combination of the proposed effective CdZnSeS/ZnS QDs synthesis and modification methods shows the prospect of their implementation as basic luminescent material for a wide range of applications.

Chiroptical Properties of Semiconducting Nanoplatelets Functionalized by Tartrate Derivatives.

Inducing chirality in semiconductor nanoparticles is a recent trend motivated by the possible applications in circularly polarized light emission, spintronics, or stereoselective synthesis. However, the previous reports on CdSe nanoplatelets (NPLs) exclusively rely on cysteine or its derivatives as chiral ligands to induce optical activity. Here, we show a strong induction of chirality with derivatives of tartaric acid obtained by a single-step synthesis. The ligand exchange procedure in organic solvent was optimized for five-monolayer (5 ML) NPLs but can also be performed on 4, 3, and 2 ML. We show that the features of the CD spectra change with structural modification of the ligands and that these chiral ligands interact mainly with the first light-hole (lh1) band rather than the first heavy-hole (hh1) band, contrary to cysteine. This result suggests that chiroptical properties could be used to probe CdSe nanoplatelets' surface ligands.

Modified surface ligand management of CsPbI3 perovskite quantum dots enables efficient and stable electroluminescent solar cells

Solution-processed CsPbI3 perovskite quantum dots (PQDs) have attracted enormous attention in both photovoltaic and electroluminescent applications in recent years. However, the surface defects of CsPbI3 PQDs in the ligand exchange procedure still suffer the challenge of imperfect passivation, leading to poor device performance and ambient stability. In this work, we propose a modified surface ligand management to deposit CsPbI3 PQD films using a layer-by-layer (LBL) solid-state exchange strategy, and its applications in photovoltaic and electroluminescent devices are studied. The conjugated phenethylammonium iodide (PEAI) ligand, acting as a short-chain ligand with a phenyl group (PEA+ ion) for encapsulating the CsPbI3 PQDs during the LBL procedure, which can both realize enhanced inter-dot coupling and defects passivation compared with conventional post-treatments. We further demonstrate the balanced transport and injection of electrons and holes within the PEAI-LBL based CsPbI3 PQD films. With this approach, the CsPbI3 PQD solar cells based on PEAI-LBL yielded a champion power conversion efficiency (PCE) of up to 14.18% with a high open voltage of 1.23 V, along with obviously electroluminescent red emission properties in one device. Meanwhile, the unencapsulated devices exhibited excellent stability under a high-humidity environment. This strategy should accelerate advancement in utilizing PQDs for bifunctional optoelectronic applications.

Superparamagnetic Nanoparticles with Phosphorescent Complexes as Hybrid Contrast Agents: Integration of MRI and PLIM

Two different hybrid nanosystems are prepared by loading highly crystalline, monodisperse magnetite nanocubes (MNCs) with phosphorescent Pt(II) complexes (PtCxs). One involves the encapsulation of the hydrophobic PtCx1 within an amphiphilic comb polymer (MNC@poly(maleic anhydride‐alt‐1‐octadecene) [PMAO]–PtCx1), whereas the other involves the direct binding of the hydrophilic PtCx2 to the surface of the MNC mediated by a ligand‐exchange procedure (MNC@OH–PtCx2). Both systems are evaluated as potential candidates for multimodal imaging in magnetic resonance imaging (MRI) and photoluminescence lifetime imaging micro(spectro)scopy (PLIM). PLIM measurements on agarose phantoms demonstrate significantly longer excited‐state lifetimes compared to the short‐lived autofluorescence of biological background. Additionally, both nanosystems perform as effective MRI contrast agents (CAs): the r2* values are 3–4 times higher than for the commercial CA ferucarbotran. MNC@PMAO–PtCx1 particles also cause significant increases in r2. While the ligand exchange procedure efficiently anchors PtCxs to the MNC surface, the polymeric encapsulation ensures higher colloidal stability, contributing to differences in PLIM and MRI outcomes. In these results, the successful integration of two complementary noninvasive imaging modalities within a single nanosystem is confirmed, serving as the impetus for further investigation of such systems as advanced multimodal–multiscale imaging agents with dual orthogonal readouts.

Preparation and Structural Characterization of Thin Films of CuInS2 by Sintering Colloidally Synthesized Nanoparticles at Moderate Temperature

Copper indium disulfide nanoparticles continue attracting attention as absorber material in light harvesting devices. The preparation of thin films by deposition of this material from colloidal solution remains challenging. Typically, colloidal semiconductor nanoparticles are surrounded by long organic ligand molecules which are required to stabilize the particles during synthesis. A common way to obtain conductive thin films is the development of ligand exchange procedures that need to be applied prior to film deposition. However, in the case of copper indium disulfide nanoparticles, appropriate procedures are still missing. Therefore, an alternative approach is investigated herein. Colloidal copper indium disulfide nanoparticles are synthesized and deposited on substrates. Instead of applying a ligand exchange procedure, thermal removal of the ligands and sintering of the inorganic film are explored. Results on the preparation of the nanoparticle films, their structural investigation, and conductivity measurements are reported.

Stabilized Perovskite Quantum Dot Solids via Nonpolar Solvent Dispersible Covalent Ligands.

The ligand exchange procedure of CsPbI3 perovskite quantum dots (PQDs) enables the fabrication of thick and conductive PQD solids that act as a photovoltaic absorber for solution-processed thin-film solar cells. However, the ligand-exchanged CsPbI3 PQD solids suffer from deterioration in photovoltaic performance and ambient stability due to the surface traps, such as uncoordinated Pb2+ sites on the PQD surface, which are generated after the conventional ligand exchange process using ionic short-chain ligands dissolved in polar solvents. Herein, a facile surface stabilization is demonstrated that can simultaneously improve the photovoltaic performance and ambient stability of CsPbI3 PQD photovoltaic absorber using covalent short-chain triphenylphosphine oxide (TPPO) ligands dissolved in a nonpolar solvent. It is found that the TPPO ligand can be covalently bound to uncoordinated Pb2+ sites and the nonpolar solvent octane can completely preserve the PQD surface components. Owing to their synergetic effects, the CsPbI3 PQD photovoltaic absorber stabilized using the TPPO ligand solution dissolved in octane exhibit higher optoelectrical properties and ambient stability than the control absorber. Consequently, CsPbI3 PQD solar cells composed of PQD photovoltaic absorbers fabricated via surface stabilization strategy provide an improved power conversion efficiency of 15.4% and an enhanced device stability.

83‐1: Improved performance of EL‐QD display through surface modified QDs and inorganic nanoink

We demonstrated the ligand exchange procedure on the InP base green QDs and Zn(Mg)O surface to improve of efficiency at EL‐QDs device. Performace of EL‐QDs device was imporved by control of electron mobility and chargen balance through ligand exchange in QDs surface. Moverover, we can prevented QD aggregation of EML throgh surface modification of electron transfer nanoparticles on inverted top emitting device.

Colloidal-ALD-Grown Metal Oxide Shells Enable the Synthesis of Photoactive Ligand/Nanocrystal Composite Materials.

Colloidal nanocrystals (NCs) are ideal materials for a variety of applications and devices, which span from catalysis and optoelectronics to biological imaging. Organic chromophores are often combined with NCs as photoactive ligands to expand the functionality of NCs or to achieve optimal device performance. The most common methodology to introduce these chromophores involves ligand exchange procedures. Despite their ubiquitous nature, ligand exchanges suffer from a few limitations, which include reversible binding, restricted access to binding sites, and the need for purification of the samples, which can result in loss of colloidal stability. Herein, we propose a methodology to bypass these inherent issues of ligand exchange through the growth of an amorphous alumina shell by colloidal atomic layer deposition (c-ALD). We demonstrate that c-ALD creates colloidally stable composite materials, which comprise NCs and organic chromophores as photoactive ligands, by trapping the chromophores around the NC core. As representative examples, we functionalize semiconductor NCs, which include PbS, CsPbBr3, CuInS2, Cu2-xX, and lanthanide-based upconverting NCs, with polyaromatic hydrocarbons (PAH) ligands. Finally, we prove that triplet energy transfer occurs through the shell and we realize the assembly of a triplet exciton funnel structure, which cannot be obtained via conventional ligand exchange procedures. The formation of these organic/inorganic hybrid shells promises to synergistically boost catalytic and multiexcitonic processes while endowing enhanced stability to the NC core.

A fluoride-induced aggregation test to quickly assess the efficiency of ligand exchange procedures from citrate capped AuNPs

HypothesisCitrate capped gold nanoparticles (AuNPs-citrate) are the starting material for most of the academic and industrial applications using gold nanoparticles. AuNPs-citrate must usually be functionalized with organic (bio)molecules, through a ligand exchange process, to become suitable for the envisaged application. The evaluation of the efficiency of the ligand-exchange process with a simple and convenient procedure is challenging. ExperimentsFluoride was used to evaluate the efficiency of a ligand exchange process from AuNPs-citrate with five standard types of ligands. The relationship between the aggregation level of the AuNPs exposed to fluoride and the amount of residual citrate ligands at the surface of the AuNPs was studied. The fluoride-induced aggregation process was characterized with various techniques such as TEM, UV-Vis, ATR-FTIR or MANTA and then used to quickly identify the optimal conditions for the functionalization of AuNPs-citrate with a new ligand, i.e. a PEGylated calixarene-tetradiazonium salt (X4-(PEG)4). FindingsIt was observed that the fluoride-induced aggregation of AuNPs is proportional to the efficiency of the ligands exchange. We believe that these results could benefit to everyone engineering AuNPs for advanced applications, as the fluoride-aggregation of AuNPs can be used as a general and versatile quality test to verify the coating density of organic (bio)molecules on AuNPs.

The Chemistry of Phenylimidotechnetium(V) Complexes with Isocyanides: Steric and Electronic Factors

Organometallic approaches are of ongoing interest for the development of novel functional 99mTc radiopharmaceuticals, while the basic organotechnetium chemistry seems frequently to be little explored. Thus, structural and reactivity studies with the long-lived isotope 99Tc are of permanent interest as the foundation for further progress in the related radiopharmaceutical research with this artificial element. Particularly the knowledge about the organometallic chemistry of high-valent technetium compounds is scarcely developed. Here, phenylimido complexes of technetium(V) with different isocyanides are introduced. They have been synthesized by ligand-exchange procedures starting from [Tc(NPh)Cl3(PPh3)2]. Different reactivity patterns and products have been obtained depending on the steric and electronic properties of the individual ligands. This involves the formation of 1:1 and 1:2 exchange products of Tc(V) with the general formulae [Tc(NPh)Cl3(PPh3)(isocyanide)], cis- or trans-[Tc(NPh)Cl3(isocyanide)2], but also the reduction in the metal and the formation of cationic technetium(I) complex of the formula [Tc(isocyanide)6]+ when p-fluorophenyl isocyanide is used. The products have been studied by single-crystal X-ray diffraction and spectroscopic methods, including IR and multinuclear NMR spectroscopy. DFT calculations on the different isocyanides allow the prediction of their reactivity towards electron-rich and electron-deficient metal centers by means of the empirical SADAP parameter, which has been derived from the potential energy surface of the electron density on their potentially coordinating carbon atoms.

Niobium and Tantalum Halocyanide Clusters: The Complete Family.

Synthetic procedures providing straightforward access to the whole family of Nb and Ta halide clusters with terminal cyanide ligands have been developed. Corresponding [M6X12(CN)12]4- (M = Nb, Ta; X = Cl, Br) can be accessed by ligand-exchange procedures from K4Nb6X18 (X = Cl, Br) and Bu4NCN, (Et4N)2[Ta6Cl18] and Bu4NCN and from [Ta6Br12(H2O)4Br2]·4H2O and KCN in moderate to high yields (50-80%). The products were isolated as Bu4N salts. The compounds were investigated both experimentally and by quantum chemistry, revealing correlations between structural, electrochemical, electrostatic, electronic, and topological features as a function of type of metal, halide, and charge.

Fe3O4@Au@Cu2−xS Heterostructures Designed for Tri‐Modal Therapy: Photo‐ Magnetic Hyperthermia and 64Cu Radio‐Insertion

Here, the synthesis and proof of exploitation of three-material inorganic heterostructures made of iron oxide-gold-copper sulfide (Fe3 O4 @Au@Cu2- x S) are reported. Starting with Fe3 O4 -Au dumbbell heterostructure as seeds, a third Cu2- x S domain is selectively grown on the Au domain. The as-synthesized trimers are transferred to water by a two-step ligand exchange procedure exploiting thiol-polyethylene glycol to coordinate Au and Cu2- x S surfaces and polycatechol-polyethylene glycol to bind the Fe3 O4 surface. The saline stable trimers possess multi-functional properties: the Fe3 O4 domain, of appropriate size and crystallinity, guarantees optimal heating losses in magnetic hyperthermia (MHT) under magnetic field conditions of clinical use. These trimers have indeed record values of specific adsorption rate among the inorganic-heterostructures so far reported. The presence of Au and Cu2- x S domains ensures a large adsorption which falls in the first near-infrared (NIR) biological window and is here exploited, under laser excitation at 808nm, to produce photo-thermal heat alone or in combination with MHT obtained from the Fe3 O4 domain. Finally, an intercalation protocol with radioactive 64 Cu ions is developed on the Cu2- x S domain, reaching high radiochemical yield and specific activity making the Fe3 O4 @Au@Cu2- x S trimers suitable as carriers for 64 Cu in internal radiotherapy (iRT) and traceable by positron emission tomography (PET).

Photo-Responsive Self-Assembly of Plasmonic Magnetic Janus Nanoparticles.

Stimuli-responsive self-assembly of nanoparticles is a versatile approach for the bottom-up fabrication of adaptive and functional nanomaterials. For this purpose, anisotropic building blocks are of particular importance due to the unique shapes and structures that can be obtained upon self-assembly. Here, we demonstrate the photo-responsive self-assembly of plasmonic magnetic "dumbbell" Janus nanoparticles (Au-Fe3O4) via the host-guest interaction of the supramolecular host cyclodextrin and the molecular photoswitch arylazopyrazole. We developed efficient ligand exchange procedures that enable the introduction of functional ligands, respectively, to the surface of the gold or magnetite core of the dumbbell. Our results indicate that distinct nanoparticle superstructures arise in aqueous solutions if nanoparticle aggregation is crosslinker-induced or self-induced and that the reversible formation and fragmentation of the superstructures can be modulated with light.

Influence of polystyrene ligand length on the spatial arrangement of quantum dots within PS-b-PEO micelles

The spatial arrangement of functional inorganic nanoparticles within polymer micelles is essential to the nanocomposite performances. Polystyrene (PS) of different lengths (PS24, PS91 and PS163) are grafted onto the surface of fluorescent CdSe/CdS core/shell quantum dots (QDs) through ligand exchange procedure, and their grafting density decreases from 2.80 to 0.54, 0.18 chains/nm2 with increase of PS ligand length. Under two competing effects, i.e. wettability between QDs and block copolymer PS120-b-PEO318 and the attraction between QDs, the precise location of PS-capped QDs inside the co-assemblies can be regulated by the length of PS ligands. The low grafting density of PS163 on the QD surface cannot overcome the van der Waals and hydrophobic attraction between QDs and cause the local aggregation of QDs within the co-assemblies. On the contrary, short PS24 ligands with high grafting density can avoid QD aggregation, but exhibit poor wettability with copolymer, which confines the QDs in the central portion of the core of co-assemblies. PS91 ligands with medium grafting density have good wettability with block copolymer and facilitate the homogeneous distribution of QDs inside the cores of co-assemblies. Furthermore, the influence of stirring time and water addition rate on the structure of co-assemblies is also investigated.

Long circulating tracer tailored for magnetic particle imaging.

Superparamagnetic iron oxide nanoparticle (SPION) tracers possessing long blood circulation time and tailored for magnetic particle imaging (MPI) performance are crucial for the development of this emerging molecular imaging modality. Here, single-core SPION MPI tracers coated with covalently bonded polyethyelene glycol (PEG) brushes were obtained using a semi-batch thermal decomposition synthesis with controlled addition of molecular oxygen, followed by an optimized PEG-silane ligand exchange procedure. The physical and magnetic properties, MPI performance, and blood circulation time of these newly synthesized tracers were compared to those of two commercially available SPIONs that were not tailored for MPI but are used for MPI: ferucarbotran and PEG-coated Synomag®-D. The new tailored tracer has MPI sensitivity that is ~3-times better than the commercial tracer ferucarbotran and much longer circulation half-life than both commercial tracers (t1/2=6.99 h for the new tracer, vs t1/2=0.59 h for ferucarbotran, and t1/2=0.62 h for PEG-coated Synomag®-D).

One-pot synthesis of P3HT–CdE (E=S, Se, Te) nanocomposites using conjugated polymer-grafted precursors

A simple one-pot synthetic strategy toward crafting semiconductor organic–inorganic nanocomposites composed of conjugated polymer poly(3-hexylthiphene) (P3HT) in close contact with CdE (E=S, Se, and Te) nanocrystals was introduced. Bifunctional ligand 4-azidobenzoic acid (BA-N3) that possesses two end functionalities at each end was employed, enabling the coordination of BA-N3 with Cd first to yield Cd-carboxylic acid complexes (Cd-BA-N3) followed by the subsequent click reaction between Cd-BA-N3 and ethynyl-terminated P3HT (P3HT–≡) to produce P3HT-grafted Cd complexes (Cd-BA-P3HT). Finally, injection of precursors resulted in P3HT-tethered CdE NC (E=S, Se, and Te) nanocomposites. The success of click reaction was confirmed by the Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy measurements. The photophysical properties such as charge transfer characteristics were corroborated with absorbance and photoluminescence characterization. Notably, this strategy circumvents the use of insulating fatty ligands, thus dispensing the need for tedious ligand exchange procedure.

PH-dependent fluorescence of thiol-coated CdSe/CdS quantum dots in an aqueous phase

The results presented in this paper show how the optical properties and colloidal stability of quantum dots (QDs) vary depending on pH conditions. For this investigation, as-synthesized hydrophobic CdSe/CdS QDs were transferred to an aqueous medium by surface modification with 3-mercaptopropionic acid. The ligand exchange procedure was applied under three different pH conditions: acidic, neutral and alkaline, to obtain three kinds of hydrophilic QDs dispersed in phosphate buffer. The efficiency of the functionalization of QDs was estimated based on the changes in ABS and the highest value was obtained under acidic conditions (45%). The efficiency of photoluminescence (PL) was also best preserved under these conditions, although it was 30 times less than the PL of hydrophobic QDs. Then, all three kinds of hydrophilic QDs were dispersed in solutions with a wide range of pH (2–12) and investigated by absorbance and PL measurements. The results show that QDs subjected to a ligand exchange procedure are characterized by intensive PL at the selected pH values, which correspond to pKa of the ligand. This phenomenon is independent of the pH at which the ligand exchange procedure is conducted. Moreover, it was found that the PL intensity is preserved during the experiment for QDs functionalized under neutral conditions, whereas it decreases for acidic and increases for alkaline conditions.

Colloidal Bi-Doped Cs2Ag1-x Na x InCl6 Nanocrystals: Undercoordinated Surface Cl Ions Limit their Light Emission Efficiency.

Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1–xNaxInCl6NCs via nuclear magnetic resonance analysis. This material, in its bulk form, was found to have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide double perovskites. Our results show that both amines and carboxylic acids are present and homogeneously distributed over the surface of the NCs. Notably, even for an optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine, a maximum PLQY value of only 37% is reached, with no further improvements observed when exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different ammonium halides, thiocyanates and sulfonic acids). Our density functional theory calculations indicate that, even with the best ligands combination, a small fraction of unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher defect tolerance. This was corroborated by our transient absorption measurements, which showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap states) competes with their localization at the AgCl6 octahedra, from where, instead, they can undergo an optically active recombination yielding the observed PL emission. Our results highlight that alternative surface passivation strategies should be devised to further optimize the PLQY of double perovskite NCs, which might include their incorporation inside inorganic shells.

Surface modification of cadmium-based nanoparticles with d-penicillamine\u2014study of pH influence on ligand exchange reaction

Semiconducting nanoparticles (NPs) find applications in many fields, with a recent focus on medicine and biology. Functionalization of the surface of NPs is necessary, and one of the most commonly employed techniques is ligand exchange (LE). In this paper, the study of pH influence on LE reaction for different types of cadmium-based NPs (quantum dots, nanorods, and nanoplates) is presented. Hydrophobic NPs were transferred to the non-organic medium by functionalization with d-penicillamine (DPA). The LE procedure was conducted at four different pH levels (4, 7, 9, and 11), and obtained hydrophilic NPs were dispersed in phosphate buffer. Results show that the most effective procedure resulted from a reaction carried at pH = 4; however, NPs with higher photoluminescence intensity were obtained when pH = 11 was used. Comparable emission was achieved from samples at pH = 4 and pH = 9. The least effective transfer, resulting in unstable NPs, occurred when the procedure was conducted at pH = 7.

Sodium Hexametaphosphate: An Inexpensive Inorganic Polyelectrolyte “Primer” For Upconverting Nanoparticles/Mesoporous Silica Core‐Shell Synthesis

AbstractWe introduce a method for depositing a uniform mesoporous SiO2 layer onto upconverting nanoparticles (UCNPs) following a two step approach. First, thermolysis synthesized hydrophobic oleate‐capped UCNP were subjected to a ligand exchange procedure with sodium hexamethaphosphate (HMP) in order to obtain hydrophilic and exceptionally stable colloidal particles. In a second step, a uniform mesoporous SiO2 shell was anchored to the HMP‐UCNP using cetyltrimethylammonium bromide (CTAB) as a porogen agent. These porous layers are mesosotructured, chemically reactive and do not change the original optical properties of the UCNP. Moreover, anchoring HMP to the nanocrystal surface favors the formation of single UCNP@mesoporous SiO2 core‐shell entities with yields up to 86%.