Supramolecular Chirality from Hierarchical Self-Assembly of Atomically Precise Silver Nanoclusters Induced by Secondary Metal Coordination

Bi, Yuting; Wang, Zhi; Liu, Tong; Sun, Di; Godbert, Nicolas; Li, Hongguang; Hao, Jingcheng; Xin, Xia

doi:10.1021/acsnano.1c03824

Cited by 59 publications

(49 citation statements)

References 54 publications

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“…The variation of the CD spectra after drying indicated that the evaporation of the solvent (water in this case) has an obvious influence on the chirality of the sample, which is reminiscent of the evaporation‐induced changes of the supramolecular chirality of Ag 9 ‐NCs/Ba 2+ hybrid. [ 39 ]…”

Section: Resultsmentioning

confidence: 99%

“…We realized that the CD spectra in the current case have good repeatability, which is in sharp contrast to the uncontrollable data observed in systems where supramolecular chirality is dominant. [ 36,39 ] Examinations on the long‐range order of the crystals from Ag 9 ‐NCs/ l ‐TrA hybrid by small‐angle X‐ray scattering (SAXS) measurements (Figure S8, Supporting Information) showed that the scattering pattern is quite similar to those of Ag 9 ‐NCs‐based hydrogel or precipitates induced by achiral organic or inorganic acids where the CD spectra were also found to be uncontrollable (Figure S9, Supporting Information). [ 40,45 ] These observations indicated that the well‐resolved CD signals of the Ag 9 ‐NCs/TrA cocrystals are unlikely from the supramolecular chirality.…”

Section: Resultsmentioning

confidence: 99%

“…However, if the thermal fluctuation of mba 2– was slowed down by, for example, the addition of Ba 2+ , the transient chirality produced by the asymmetric distribution of the ligands along the horizontal mirror of the cluster could be fixed, which led to configurational chirality of individual cluster and finally resulted in the appearance of chirality at different length scales. [ 39 ]…”

Section: Introductionmentioning

confidence: 99%

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Circularly Polarized Phosphorescence from Cocrystallization of Atomic Precise Silver Nanoclusters with Tartaric Acid

Feng

Wang

Sun

et al. 2022

Advanced Optical Materials

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Recently, chirality was successfully introduced to rare earth complexes, which have long afterglow phosphorescence, by ball-milling with l/d-cysteine, leading to CPP with a dissymmetry factor (g lum ) up to 10 −2 . [16] CPP from multiple metal centers has also been achieved by the preparation of a homochiral metal-organic framework. [17] Despite these fantastic examples, the candidates for creating CPP are still limited. New candidates with a long lifetime and intrinsic phosphorescence are urgently needed to widen the family of CPP materials and broaden the scope of their applications.Metal nanoclusters (NCs) are intermediates between single-metal complexes and metal nanoparticles. [18,19] Metal NCs, especially those formed by the complexation of metal ions with organic ligands, could have atomic precision proved by single-crystal X-ray diffraction analysis. Their photoluminescence is normally weak in dilute dispersions or amorphous state, which is disadvantageous for the construction of CPP materials. However, this drawback could be overcome by lowering the temperature or forcing them to form highly ordered supramolecular structures. [20] In the latter case, in most cases, the emission is characterized by a relatively long lifetime of microseconds that could be assigned to phosphorescence in nature. For the chirality which is another necessity to induce CPP, chiral organic ligands were routinely adopted during the preparation of the metal NCs. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Based on these efforts, a few metal NCs that exhibit CPP in solid states have been successfully created, including gold, [27][28][29] silver, [30,31] and copper [32][33][34][35] NCs.In terms of the chirality of a given system, the building blocks are unnecessarily chiral, which has been confirmed by chiral supramolecular self-assemblies formed by achiral organic molecules, such as those with C 3 -symmetry. [36][37][38] However, this rule has not been demonstrated for metal NCs until very recently. [39] The breakthrough came from the assembly of watersoluble silver NCs ((NH 4 ) 9 [Ag 9 (mba) 9 ], H 2 mba = 2-mercaptobenzoic acid, abbreviated to Ag 9 -NCs hereafter), which were facilely obtained by coordination of Ag(I) with 2-mercaptobenzoic acid (H 2 mba) in water in the presence of ammonia-water (Figure 1a). Single-crystal X-ray diffraction analysis showed each cluster has a core of nine Ag(I) ions that resembles a triangular prism comprising three Ag 3 trigons. The cluster has a C 3 axis that passes Recently, advanced optical materials with circularly polarized phosphorescence (CPP) have attracted much attention. However, such materials are limited due to the difficulty of preparation and the scarcity of precursors. Herein, CPP materials are constructed for the first time using water-soluble, pseudo-chiral silver nanoclusters with atomic precision ((NH 4 ) 9 [Ag 9 (mba) 9 ], H 2 mba = 2-mercaptobenzoic acid, abbreviated to Ag 9 -NCs hereafter). Induced by the complexation of l-or d-tartaric acid (TrA) through h...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Circularly Polarized Phosphorescence from Cocrystallization of Atomic Precise Silver Nanoclusters with Tartaric Acid

Feng

Wang

Sun

et al. 2022

Advanced Optical Materials

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“…The synthesis, purification and detailed characterization of Ag 9 -NCs can be found in literature [ 6 , 25 ]. DD-5 was purchased from GL Biochem Ltd. (Shanghai, China) and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Supramolecular Self-Assembly of Atomically Precise Silver Nanoclusters with Chiral Peptide for Temperature Sensing and Detection of Arginine

Wang

Sun

et al. 2022

Nanomaterials

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Metal nanoclusters (NCs) as a new type of fluorescent material have attracted great interest due to their good biocompatibilities and outstanding optical properties. However, most of the studies on metal NCs focus on the synthesis, atomic or molecular assembly, whereas metal NCs ability to self-assemble to higher-level hierarchical nanomaterials through supramolecular interactions has rarely been reported. Herein, we investigate atomic precise silver NCs (Ag9-NCs, [Ag9(mba)9], where H2mba = 2-mercaptobenzoic acid) and peptide DD-5 were used to induce self-assembly, which can trigger an aggregation-induced luminescence (AIE) effect of Ag9-NCs through non-covalent forces (H-bond, π–π stacking) and argentophilic interactions [Ag(I)–Ag(I)]. The large Stokes shift (~140 nm) and the microsecond fluorescence lifetime (6.1 μs) indicate that Ag9-NCs/DD-5 hydrogel is phosphor. At the same time, the chirality of the peptide was successfully transferred to the achiral Ag9-NCs because of the supramolecular self-assembly, and the Ag9-NCs/DD-5 hydrogel also has good circularly polarized luminescence (CPL) properties. In addition, Ag9-NCs/DD-5 luminescent hydrogel is selective and sensitive to the detection of small biological molecule arginine. This work shows that DD-5 successfully induces the self-assembly of Ag9-NCs to obtain high luminescent gel, which maybe become a candidate material in the fields of sensors and biological sciences.

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“…This study revealed that the ligands’ regiospecific distribution and arrangement formed the anisotropic growth. A very recent study reported the formation of chiral assembly from achiral, atomically precise Ag 9 NCs [ 105 ]. Here, a second metal ion, Ba 2+ , facilitated the assembly process, and thus nanotubes with chiral cubic lattice were obtained.…”

Section: Guided Assembly By External Factorsmentioning

confidence: 99%

Self-Assembled Metal Nanoclusters: Driving Forces and Structural Correlation with Optical Properties

Kolay

Bain²,

Maity

et al. 2022

Nanomaterials

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Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications.

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Supramolecular Chirality from Hierarchical Self-Assembly of Atomically Precise Silver Nanoclusters Induced by Secondary Metal Coordination

Cited by 59 publications

References 54 publications

Circularly Polarized Phosphorescence from Cocrystallization of Atomic Precise Silver Nanoclusters with Tartaric Acid

Circularly Polarized Phosphorescence from Cocrystallization of Atomic Precise Silver Nanoclusters with Tartaric Acid

Supramolecular Self-Assembly of Atomically Precise Silver Nanoclusters with Chiral Peptide for Temperature Sensing and Detection of Arginine

Self-Assembled Metal Nanoclusters: Driving Forces and Structural Correlation with Optical Properties

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