Direct and Indirect Evolution of Photoluminescent Semiconductor CdS Magic-Size Clusters through Their Precursor Compounds.

Colloidal semiconductor II-VI metal chalcogenide (ME) magic-size clusters (MSCs) exhibit either an optical absorption singlet or doublet. In the latter case, a sharp photoluminescence (PL) signal is observed. Whether the PL-inactive MSCs transform to the PL-active ones is unknown. We show that PL-inactive CdS MSC-322 transforms to PL-active CdS MSC-328 and MSC-373 in the presence of acetic acid (HOAc). MSC-322 displays a sharp absorption at ≈322 nm, whereas MSC-328 and MSC-373 both have broad absorptions respectively around 328 and 373 nm. In a reaction of cadmium myristate and S powder in 1-octadecene, MSC-322 develops; with HOAc, MSC-328 and MSC-373 are present. We propose that the MSCs evolve from their relatively transparent precursor compounds (PCs). The PC-322 to PC-328 quasi-isomerization involves monomer substitution, while monomer addition occurs for the PC-328 to PC-373 transformation. Our findings suggest that S dominates the precursor self-assembly quantitatively, and ligand-bonded Cd mainly controls MSC optical properties.

Direct and Indirect Pathways of CdTeSe Magic-Size Cluster Isomerization Induced by Surface Ligands at Room Temperature.

The field of isomerization reactions for colloidal semiconductor magic-size clusters (MSCs) remains largely unexplored. Here, we show that MSCs isomerize via two fundamental pathways that are regulated by the acidity and amount of an incoming ligand, with CdTeSe as the model system. When MSC-399 isomerizes to MSC-422 at room temperature, the peak red-shift from 399 to 422 nm is continuous (pathway 1) and/or stepwise (pathway 2) as monitored in situ and in real time by optical absorption spectroscopy. We propose that pathway 1 is direct, with intracluster configuration changes and a relatively large energy barrier. Pathway 2 is indirect, assisted by the MSC precursor compounds (PCs), from MSC-399 to PC-399 to PC-422 to MSC-422. Pathway 1 is activated when PC-422 to MSC-422 is suppressed. Our findings unambiguously suggest that when a change occurs directly on a nanospecies, its absorption peak continuously shifts. The present study provides an in-depth understanding of the transformative behavior of MSCs via ligand-induced isomerization upon external chemical stimuli.

Transformations of Magic-Size Clusters via Precursor Compound Cation Exchange at Room Temperature.

The transformation of colloidal semiconductor magic-size clusters (MSCs) from zinc to cadmium chalcogenide (ZnE to CdE) at low temperatures has received scant attention. Here, we report the first room-temperature evolution of CdE MSCs from ZnE samples and our interpretation of the transformation pathway. We show that when prenucleation stage samples of ZnE are mixed with cadmium oleate (Cd(OA)2), CdE MSCs evolve; without this mixing, ZnE MSCs develop. When ZnE MSCs and Cd(OA)2 are mixed, CdE MSCs also form. We propose that Cd(OA)2 reacts with the precursor compounds (PCs) of the ZnE MSCs but not directly with the ZnE MSCs. The cation exchange reaction transforms the ZnE PCs into CdE PCs, from which CdE MSCs develop. Our findings suggest that in reactions that lead to the production of binary ME quantum dots, the E precursor dominates the formation of binary ME PCs (M = Zn or Cd) to have similar stoichiometry. The present study provides a much more profound view of the formation and transformation mechanisms of the ME PCs.

Manipulating Reaction Intermediates to Aqueous-Phase ZnSe Magic-Size Clusters and Quantum Dots at Room Temperature.

It is not resolved which model describes better the aqueous-phase nucleation and growth of semiconductor quantum dots (QDs), the classical one-step one or the nonclassical multi-step one. Here, we design a room-temperature reaction to trap reaction intermediates in the prenucleation stage of ZnSe QDs (as a model system). We show that the trapped intermediate can transform to magic-size clusters (MSCs) via intra-molecular reorganization and can fragment to enable the growth of QDs. The MSCs exhibit a sharp optical absorption peaking at 299 nm, labelled MSC-299. The intermediate, the precursor compound (PC-299) of MSC-299, is optically transparent at 299 nm and to longer wavelengths. This intermediate forms in various Zn and Se reaction systems. The present study provides unambiguous evidence that the nonclassical and classical pathways are both necessary to explain the nucleation and growth of aqueous-phase QDs, with the former pathway favored more by high reaction concentrations.

A Real-Time In Situ Demonstration of Direct and Indirect Transformation Pathways in CdTe Magic-Size Clusters at Room Temperature.

The transformations of colloidal semiconductor magic-size clusters (MSCs) are expected to occur with only discrete, step-wise redshifts in optical absorption. Here, we challenge this assumption presenting a novel, conceptually different transformation, for which the redshift is continuous. In the room-temperature transformation from CdTe MSC-448 to MSC-488 (designated by the peak wavelengths in nanometer), the redshift of absorption monitored in situ displays distinctly continuous and/or step-wise behavior. Based on conclusive evidence provided by real-time experiments, the former transformation is apparently direct and intra-cluster with a relatively large energy barrier. The latter transformation is indirect and assisted by MSC precursor compounds (PCs). The former transformation follows the latter often, being predominant at a relatively high temperature. The present findings encourage a reconsideration of the absorption redshift reported previously for transformations of binary II-VI MSCs, together with the pathway associated without the increase of cluster mass.

Size matters: Steric hindrance of precursor molecules controlling the evolution of CdSe magic-size clusters and quantum dots.

Little is known about how to precisely promote the selective production of either colloidal semiconductor metal chalcogenide (ME), magic-size clusters (MSCs), or quantum dots (QDs). Recently, a two-pathway model has been proposed to comprehend their evolution; here, we reveal for the first time that the size of precursors plays a decisive role in the selected evolution pathway of MSCs and QDs. With the reaction of cadmium myristate (Cd(MA)2) and tri-n-octylphosphine selenide (SeTOP) in 1-octadecene (ODE) as a model system, the size of Cd precursors was manipulated by the steric hindrance of carboxylic acid (RCOOH) additive. Without RCOOH, the reaction produced both CdSe MSCs and QDs (from 100 to 240 °C). With RCOOH, the reaction produced MSCs or QDs when R was small (such as CH3-) or large (such as C6H5-), respectively. According to the two-pathway model, the selective evolution is attributed to the promotion and suppression of the self-assembly of Cd and Se precursors, respectively. We propose that the addition of carboxylic acid may occur ligand exchange with Cd(MA)2, causing the different sizes of Cd precursor. The results suggest that the size of Cd precursors regulates the self-assemble behavior of the precursors, which dictates the directed evolution of either MSCs or QDs. The present findings bring insights into the two-pathway model, as the size of M and E precursors determine the evolution pathways of MSCs or QDs, the understanding of which is of great fundamental significance toward mechanism-enabled design and predictive synthesis of functional nanomaterials. Electronic Supplementary Material: Supplementary material (additional optical absorption spectra, TEM, NMR, FT-IR, and XRD) is available in the online version of this article at 10.1007/s12274-022-4421-4.

A Two-Pathway Model for the Evolution of Colloidal Compound Semiconductor Quantum Dots and Magic-Size Clusters.

A fundamental understanding of formation pathways is critical to the controlled synthesis of colloidal semiconductor nanocrystals. As ultrasmall-size quantum dots (QDs) sometimes emerge in reactions along with magic-size clusters (MSCs), distinguishing their individual pathway of evolution is important, but has proven difficult. To decouple the evolution of QDs and MSCs, an unconventional, selective approach has been developed, along with a two-pathway model that provides a fundamental understanding of production selectivity. For on-demand production of either ultrasmall QDs or MSCs, the key enabler is in how to allow a reaction to proceed in the time prior to nucleation and growth of QDs. In this prenucleation stage, an intermediate compound forms, which is the precursor compound (PC) to the MSC. Here, the two-pathway model and the manipulation of such PCs to synthesize either ultrasmall QDs or binary and ternary MSCs are highlighted. The two-pathway model will assist the development of nucleation theory as well as provide a basis for a mechanism-enabled design and predictive synthesis of functional nanomaterials.

Transformation Pathways in Colloidal CdTeSe Magic-Size Clusters.

A rarely studied transformation in colloidal ternary magic-size clusters (MSCs) is addressed. We report the first observation of the transformation from ternary CdTeSe MSC-399 to MSC-422, which occurs at room temperature. These two MSC types display sharp optical absorption resonances at 399 and 422 nm, respectively, and are related in that they are quasi isomers, together with their counterpart precursor compounds (PCs). Binary CdTe and CdSe samples were prepared in the prenucleation stage also called the induction period (IP). After they were mixed and placed in a mixture of toluene and octylamine, the transformation was found to take place and to be assisted by the addition of the CdSe IP sample. A binary IP sample contains corresponding binary PCs and monomers (Mo) and fragments (Fr). We argue that the transformation pathway is enabled by the corresponding ternary PCs, involving the substitution reaction, namely CdTeSe PC-399 + CdSe (Mo/Fr)-1 ⇒ CdTeSe PC-422 + CdSe (Mo/Fr)-2. The present study provides an in-depth understanding of the formation characteristics of the MSCs.

Transformation Pathway from CdSe Magic-Size Clusters with Absorption Doublets at 373/393†nm to Clusters at 434/460†nm.

Divergent interpretations have appeared in the literature regarding the structural nature and evolutionary behavior for photoluminescent CdSe nanospecies with sharp doublets in optical absorption. We report a comprehensive description of the transformation pathway from one CdSe nanospecies displaying an absorption doublet at 373/393 nm to another species with a doublet at 433/460 nm. These two nanospecies are zero-dimensional (0D) magic-size clusters (MSCs) with 3D quantum confinement, and are labeled dMSC-393 and dMSC-460, respectively. Synchrotron-based small-angle X-ray scattering (SAXS) returns a radius of gyration of 0.92 nm for dMSC-393 and 1.14 nm for dMSC-460, and indicates that both types are disc shaped with the exponent of the SAXS form factor equal to 2.1. The MSCs develop from their unique counterpart precursor compounds (PCs), which are labeled PC-393 and PC-460, respectively. For the dMSC-393 to dMSC-460 transformation, the proposed PC-enabled pathway is comprised of three key steps, dMSC-393 to PC-393 (Step 1), PC-393 to PC-460 (Step 2 involving monomer addition), and PC-460 to dMSC-460 (Step 3). The present study provides a framework for understanding the PC-based evolution of MSCs and how PCs enable transformations between MSCs.

Reversible Transformations at Room Temperature among Three Types of CdTe Magic-Size Clusters.

We report the first observation of the reversible transformations that occur among three types of CdTe magic-size clusters (MSCs) in dispersion at room temperature and discuss our understanding of the transformation pathway. The reversible transformations were achieved with CdTe prenucleation stage samples, which were prepared with reactions of cadmium oleate [Cd(OA)2] and tri-n-octylphosphine telluride in 1-octadecene and were then dispersed in mixtures of toluene and a primary amine at room temperature. Three types of OA-passivated CdTe MSCs evolved, exhibiting sharp optical absorption singlets peaking at 371, 417, and 448 nm. The MSCs and their immediate precursor compounds (PCs; with no sharp optical absorption) are labeled by the MSC absorption peak wavelengths. The transformation between MSC-371 and MSC-417 has a distinct isosbestic point at ∼385 nm and that between MSC-417 and MSC-448 at ∼430 nm. Our findings suggest that these PC-enabled reversible transformations occur through a process of quasi-isomerization, transforming between PCs and their counterpart MSCs, combined with substitution reactions that cause transformation between the two involved PCs.

Transformations Among Colloidal Semiconductor Magic-Size Clusters.

A knowledge of colloidal semiconductor magic-size clusters (MSCs) is essential for understanding how fundamental properties evolve during transformations from individual molecules to semiconductor quantum dots (QDs). Compared to QDs, MSCs display much narrower optical absorption bands; the higher cluster stability gives rise to a narrower size distribution. During the production of binary QDs such as II-VI metal (M) chalcogenide (E) ones, binary ME MSCs observed were interpreted as side products and/or the nuclei of QDs. Prior to the current development of our two-step approach followed by our two-pathway model, it had been extremely challenging to synthesize MSCs as a unique product without the nucleation and growth of QDs. With the two-step approach, we have demonstrated that MSCs can be readily engineered as a sole product at room temperature from a prenucleation stage sample, also called an induction period (IP) sample. It is important that we were able to discover that the evolution of the MSCs follows first-order reaction kinetics behavior. Accordingly, we proposed that a new type of compound, termed as "precursor compounds" (PCs) of MSCs, was produced in an IP sample. Such PCs are optically transparent at the absorption peak positions of their MSC counterparts as well as to longer wavelengths. It is thought that quasi isomerization of a single PC results in the development of one MSC.In this Account, we provide an overview of our latest advances regarding the transformations among binary CdE MSCs as well as from binary CdTe to ternary CdTeSe MSCs. Optical absorption spectroscopy has been employed to study these transformations, all of which display well-defined isosbestic points. We have proposed that these MSC to MSC transformations occur via their corresponding PCs, also called immediate PCs. It is reasonable that the as-synthesized PC (in an IP sample) and the immediate PC (in an incubated and/or diluted sample) probably have different configurations. A transformation between two PCs may involve an intermolecular reaction, with either first-order reaction kinetics or a more complicated time profile. A transformation between one immediate PC and its counterpart MSC may contain an intramolecular reaction. The present Account, which addresses the PC-enabled MSC transformations with isosbestic points probed by optical absorption spectroscopy, calls for more experimental and theoretical attention to understand these magic species and their transformation processes more precisely.

Ophthalmic Drops with Nanoparticles Derived from a Natural Product for Treating Age-Related Macular Degeneration.

There is a continuing, urgent need for an ophthalmic (eye) drop for the clinical therapy of age-related macular degeneration (AMD), a leading cause of blindness. Here, we report the first formulation of an eye drop that is effective via autophagy for AMD treatment. This eye drop is based on a single natural product derivative (ACD), which is an amphiphilic molecule containing a 6-aminohexanoate group (H2N(CH2)5COO-). We demonstrate that this eye drop reverses the abnormal angiogenesis induced in a primate model of AMD that has the pathological characteristics close to that of human AMD. The ACD molecule was self-assembled in an aqueous environment leading to nanoparticles (NPs) about 9.0 nm in diameter. These NPs were encapsulated in calcium alginate hydrogel. The resulting eye drop effectively slowed the release of ACD and displayed extended release periods in both simulated blood (pH 7.4) and inflammatory (pH 5.2) environments. We show that the eye drop penetrated both the corneal and blood-eye barriers and reached the fundus. With low cellular toxicity, the drop targeted S1,25D3-membrane-associated rapid response steroid-binding protein (1,25D3-MARRS) promoting autophagy in a dose-dependent manner. In addition, the drop inhibited cell migration and tubular formation. On the other hand, when protein 1,25D3-MARRS was knocked down, the eye drop did not exhibit such inhibition functionalities. Our study indicates that the 6-aminohexanoate group on self-assembled NPs encapsulated in hydrogel leads to the positive in vivo outcomes. The present formulation offers a promising approach for clinical treatment of human AMD.

Room-temperature formation of CdS magic-size clusters in aqueous solutions assisted by primary amines.

Aqueous-phase approaches to semiconductor CdS magic-size clusters (MSCs) and the formation pathway have remained relatively unexplored. Here, we report the demonstration of an aqueous-phase, room-temperature approach to CdS MSCs, together with an exploration of their evolution pathway. The resulting CdS MSCs display a sharp optical absorption peak at about 360 nm and are labeled MSC-360. With CdCl2 and thiourea as the respective Cd and S sources, and 3-mercarpotopropionic acid as the ligand, CdS MSC-360 develops in a mixture of a primary amine and water. We argue that the primary amine facilitates room-temperature decomposition of thiourea when CdCl2 is present, and the formation pathway of MSCs is similar to that in organic-phase approaches. Our findings show there is a viable avenue to room-temperature aqueous-phase formation of CdS MSCs. Providing explanations of the procedure developed including the formation of large aggregates, the present study represents an important advance towards a mechanistic understanding of nanocrystal synthesis.

Room-Temperature Formation Pathway for CdTeSe Alloy Magic-Size Clusters.

Little is known about the pathway of room-temperature formation of ternary CdTeSe magic-size clusters (MSCs) obtained by mixing binary CdTe and CdSe induction period samples containing binary precursor compounds (PCs) of MSCs, monomers (Ms), and fragments (Fs). Also, unestablished are dispersion effects that occur when as-mixed samples (without incubation) are placed in toluene (Tol) and octylamine (OTA) mixtures. The resulting ternary MSCs, exhibiting a sharp optical absorption peak at 399 nm, are labelled CdTeSe MSC-399, and their PCs are referred to as CdTeSe PC-399. When the amount of OTA is relatively small, single-ensemble MSC-399 evolved without either binary CdTe or CdSe MSCs. When the OTA amount is relatively large, CdTe MSC-371 appeared initially and then disappeared, while single-ensemble MSC-399 developed more deliberately. The larger the OTA amount, the more slowly these changes proceeded. The substitution reaction of CdTe PC + CdSe M/F↔CdTeSe PC-399 + CdTe M/F is proposed to be rate-determining for the MSC-399 formation in a Tol and OTA mixture. This study provides further understanding of the transformation pathway between MSCs.

Fragmentation of Magic-Size Cluster Precursor Compounds into Ultrasmall CdS Quantum Dots with Enhanced Particle Yield at Low Temperatures.

Colloidal small-size CdS quantum dots (QDs) are produced usually with low particle yield, together with side products such as the particular precursor compounds (PCs) of magic-size clusters (MSC). Here, we report our synthesis of small-size CdS QDs without the coexistence of the PC and thus with enhanced particle yield. For a conventional reaction of cadmium oleate (Cd(OA)2 ) and sulfur (S) in 1-octadecene (ODE), we show that after the formation of the PC in the pre-nucleation stage, the addition of tri-n-octylphosphine oxide (TOPO) facilitates the production of small-size QDs. We demonstrate that TOPO fragmentizes the PC that have formed, which enables the nucleation and growth of small-size QDs even at room temperature. Our findings introduce a new approach to making small-size QDs without the coexistence of the PC and with improved particle yield. Providing experimental evidence for the two-pathway model proposed for the pre-nucleation stage of colloidal binary QDs, the present study aids in the advance of non-classical nucleation theory.

Evolution of CdTe Magic-Size Clusters with Single Absorption Doublet Assisted by Adding Small Molecules during Prenucleation.

An approach is reported for the exclusive production of CdTe magic-size clusters (MSCs) that exhibit an optical absorption doublet peaking at 385/427 nm, with an explanation of the synthesis procedure. The MSCs, defined as dMSC-427, were produced from the reaction of cadmium oleate (Cd(OA)2) and tri-n-octylphosphine telluride in octadecene at 100 °C, with the addition of acetic acid (HOAc) or acetate (M(OAc)2) during the prenucleation stage (40 °C). Without such an addition or when it was performed in the postnucleation stage (100 °C), quantum dots (QDs) developed. The production of dMSC-427 or QDs is hypothesized to be related to the solubility of the Cd precursor, such as Cd(OA)1(OAc)1 or Cd(OA)2, respectively. Also, the reactions that lead to Cd(OA)1(OAc)1 are proposed. The present study provides an in-depth understanding of the two-pathway model proposed for the prenucleation stage of binary colloidal QDs, as well as of the formation of MSCs and/or QDs.

Transformation of ZnS Precursor Compounds to Magic-Size Clusters Exhibiting Optical Absorption Peaking at 269 nm.

We report our investigation on the transformation pathway from precursor compounds (PCs) to magic-size clusters (MSCs) for semiconductor ZnS. We show, for the first time, a synthetic approach to ZnS MSCs in a single-ensemble form exhibiting optical absorption peaking at 269 nm. We thus symbolize the MSCs as MSC-269. The synthesis was performed with zinc oleate (Zn(OA)2) and elemental sulfur (S) as the respective Zn and S sources and 1-octadecene (ODE) as the reaction medium. Prior to the addition of S, oleylamine (OLA) is mixed with Zn(OA)2. ZnS MSC-269 evolved at a relatively high temperature from a reaction mixture or at room temperature during a dispersion incubation of a reaction product in a solvent. Both optical absorption and NMR studies support that the evolution of colloidal semiconductor MSCs contains three different stages. The present study narrows our knowledge gap on PC-to-MSC transformations that involve a loss of ligands from the PC.

Identifying Clusters and/or Small-Size Quantum Dots in Colloidal CdSe Ensembles with Optical Spectroscopy.

It is well-known that optical absorption and photoluminescence (PL) provide information that is sensitive to the size and size distribution of colloidal binary semiconductor quantum dots (QDs). To explore the nature of reaction products, clusters, and/or small-size QDs, we show that it is important to perform as well photoluminescence excitation (PLE) spectroscopy. For two non-hot-injection reactions of cadmium oleate (Cd(OA)2) and selenium (Se) in 1-octadecene (ODE), we show that sequentially extracted products displayed a similar apparent red shift in both absorption and PL with a full width at half-maximum (fwhm) of ∼30 nm. We demonstrate that one reaction (with the presence of diphenyl phosphine (HPPh2)) produced multiple types of clusters (with slightly different optical properties) in one ensemble, while the other reaction (without HPPh2) yielded primarily small-size QDs. Our findings provide evidence for the probable existence of clusters within small-size CdSe QD products, the existence of which complicates the size determination of small-size CdSe QDs.

Four Types of CdTe Magic-Size Clusters from One Prenucleation Stage Sample at Room Temperature.

Four types of colloidal semiconductor CdTe magic-size clusters (MSCs), each of which is in a single-ensemble form, have been obtained at room temperature from a single induction period (IP) sample in dispersion. The induction period is the prenucleation stage that occurs prior to nucleation and growth of colloidal quantum dots (QDs). Three types display sharp optical absorption peaking at either 371, 417, or 448 nm, and the fourth type exhibits a sharp absorption doublet with peaks at 350 and 371 nm. These MSCs are respectively denoted as sMSC-371, sMSC-417, sMSC-448, and dMSC-371. We show that the evolution of the various MSCs is affected by the nature of their dispersions. We hypothesize that the evolution of MSCs involves their precursor compounds (PCs), which are transparent in optical absorption. The present study explores new avenues for the exclusive synthesis of four types of CdTe MSCs (with each in a single-ensemble form) and provides an improved understanding for their formation.

Photoluminescent Colloidal Nanohelices Self-Assembled from CdSe Magic-Size Clusters via Nanoplatelets.

Reports on photoluminescent colloidal semiconductor two-dimensional (2D) helical nanostructures with one-dimensional quantum confinement are relatively rare. Here, we discuss the formation of such photoluminescent nanostructures for CdSe. We show that when as-synthesized unpurified zero-dimensional (0D) CdSe magic-size clusters (MSCs) (passivated by carboxylate ligands with three-dimensional quantum confinement) are dispersed in a solvent (such as toluene or chloroform) containing hexadecylamine and then subjected to sonication, helical nanostructures are obtained, as observed by transmission electron microscopy. We demonstrate that the formation involves the self-assembly of 0D MSCs into 2D nanoplatelets, which act as intermediates. The CdSe MSCs and their self-assembled 2D nanostructures display almost identical static optical properties, namely, a sharp absorption doublet with peaks at 433 and 460 nm and a narrow emission peak at 465 nm; this is a subject for further study. This study introduces new methods for fabricating photoluminescent helical nanostructures via the self-assembly of photoluminescent MSCs.