Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Bodiuzzaman, Mohammad; Ghosh, Atanu; Sugi, Korath Shivan; Nag, Abhijit; Khatun, Esma; Varghese, Babu; Paramasivam, Ganesan; Antharjanam, P. K. Sudhadevi; Natarajan, Ganapati

doi:10.1002/anie.201809469

Cited by 87 publications

(92 citation statements)

References 33 publications

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“…From top left to bottom right: Chiral phosphine/thiolate coprotected Ag and Ag-based bimetallic NCs: [Ag 15 (TP) 4 Cl 4 ] 3+ , [239] Ag 16 (SR) 14 (DPPE) 4 , [238] Ag 23 (SR) 18 (PPh 3 ) 8 , [240] [Au 1 Ag 24 (SR) 17 (DPPM) 3 ] 2+ , [241] Pt 1 Ag 28 (SR) 18 (PPh 3 ) 4 , [242] Ag 29 (SR) 12 (PPh 3 ) 4 , [221] [Ag 32 (SR) 24 (DPPE) 5 ] 2− , [238] [Ag 32 (SR) 13 (DPPM) 5 Cl 8 ] 3+ , [243] Ag 33 (SR) 24 (PPh 3 ) 4 , [244] Ag 43 (SR) 25 (PPh 3 ) 4 , [245] [Ag 45 (SR) 16 (DPPM) 4 Br 12 ] 3+ , [243] Au 9 Ag 36 -(SR) 27 (PPh 3 ) 6 , [246] [Ag 67 (SR) 32 (PPh 3 ) 8 ] 3+ , [247] Ag 78 (SR) 42 (DPPP) 6 . [248] Achiral phosphine/thiolate coprotected Ag NCs: Ag 14 (SR) 12 -(PPh 3 ) 8 , [249] Pt 1 Ag 26 (SR) 18 (PPh 3 ) 6 , [250] Ag 38 (SR) 26 (PPh 3 ) 8 , [251] Ag 46 (SR) 24 (PPh 3 ) 8 , [245,252] Ag 50 (SR) 30 (DPPM) 6 , [253] Ag 63 (SR) 36 (PPh 3 ) 8 . [251] As shown in Scheme 5, as the involvement of phosphine in Ag NCs does not change the surface bonding, i.e., the S coordination in the outmost Ag-S-P cage is not affected, it is still the distortion of the Ag-S-P mount motifs or the Ag-S-P cages that decides the chirality of the clusters.…”

Section: Thiolate/phosphine Coprotected Ag Ncsmentioning

confidence: 99%

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Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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In chemical science, chirality is indeed one of the most extensively studied phenomena. A chiral molecule possesses a pair of enantiomers and sometimes, only one of the enantiomers is effective as a functional unit or drug. [1,2] The mechanism on how the notorious enantiomers of thalidomide lead to teratogenic newborns has been revealed recently. [3] Chirality in coordination complexes has also been generalized in detail. [4] A classic example of molecules with point chirality is that it contains an asymmetric sp 3 carbon atom which is attached with four different atoms or groups. Such a molecule is not superimposable with its mirror image, and for a simple coordination complex, a metal atom-which is at the centerserves as the role of the chiral carbon (i.e., point chirality). As a result, the relative spatial arrangement of the substituents gives either a clockwise or an anticlockwise order, corresponding to the R and S enantiomers. Of note, the R/S notation of chirality has no fixed relation to the d/l notation (for sugars and amino acids). More generally speaking, chiral object is lack of S n symmetry elements; in other words, if a mirror plane (σ) and inversion (i) are both missing in the object, then it becomes chiral. From this definition, irregular objects are all chiral. Objects of C n (with n-fold axis) or D n (with C 2 axis perpendicular to the n-fold axis) symmetry are much more appealing as long-range order is created. Along with organic chiral molecules, [2] chiral complexes, [4] and chiral supramolecular systems with autonomous self-assembly generated by intermolecular noncovalent interactions have been discussed thoroughly in previous reviews. [5-9] Chiral inorganic nanostructures, with intermediate sizes between molecules of Å and objects of micrometers, are of critical significance owing to their tremendous applications in chiral catalysis, chiroptical metamaterials, enantioseparation, biomolecular and enantiomer sensing, as well as medicine. [10-12] For chiral semiconductor nanoparticles (NPs), commonly called quantum dots (QDs), such as cadmium chalcogenides, the chiral surface ligands are attached onto the QDs through covalent bonds, [13-17] and many applications can be designed. [18] The interactions of chiral moieties attached on graphene NPs lead to their helical assembly, enriching the optical and electronic properties of these chiral nanostructures and facilitating their applications. [19-21] The studies on chiral metal NPs greatly overwhelm those on the semiconductor counterparts. Metal NPs are known to have Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand-protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic-inorganic in...

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Section: Thiolate/phosphine Coprotected Ag Ncsmentioning

confidence: 99%

“…Achiral phosphine/thiolate coprotected Ag NCs: Ag 14 (SR) 12 (PPh 3 ) 8 ,249 Pt 1 Ag 26 (SR) 18 (PPh 3 ) 6 ,250 Ag 38 (SR) 26 (PPh 3 ) 8 ,251 Ag 46 (SR) 24 (PPh 3 ) 8 ,245,252 Ag 50 (SR) 30 (DPPM) 6 ,253 Ag 63 (SR) 36 (PPh 3 ) 8 251…”

Section: Beyond the Au‐sr Nanoclustersmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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“…[ 5–8 ] Therefore, nanocluster can be represented by formulas as [M n (L) m ] q (n, m, and q denote the number of metal atoms, ligands, and charges in the nanocluster, respectively), just like the molecular compound. [ 9–20 ] Furthermore, the free electrons in nanoclusters can significantly influence their physical–chemical properties. [ 21 ] In addition, the precise compositions and well‐defined sizes of nanoclusters are also helpful for understanding the structure–property relationships which are necessary for rationally designing the nanoclusters with enhanced performance.…”

Section: Introductionmentioning

confidence: 99%

Insight of the photoluminescence of atomically precise bimetallic nanoclusters with free electrons

Yang

Zhu

2020

J Chinese Chemical Soc

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Noble-metal nanoclusters with emission properties are promising candidtes for cell imaging, biosensing, photo-therapy applications due to their ultra-small size, good photostability, and high biocompatibility. It is of great importance to realize the atomic precision of such metal nanoclusters (NCs) because they allow us to investigate the origin of fluorescence at the atomic level. However, compared to quantum dots (QDs) and organic dyes, noble metal nanoclusters usually suffered from low quantum yield, which significantly limited their applications. Doping with other metal atoms is an effective strategy to enhance the fluorescent properties of metal NCs. Therefore, bimetallic nanoclusters possess enhanced emission properties relative to their monometallic counterparts. Although a couple of reviews have existed for bimetallic nanocluster, few of them concern their emissive properties. In this context, the emissive properties of atomically precise bimetallic nanoclusters are summarized in this minireview. Synergistic effect, state of aggregation, assembly, and isomerism on the fluorescence of bimetallic clusters and structure-photoluminescence property correlations are also discussed.

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“…Recent reports on atomically precise NCs have shed light on some interesting phenomena. For example, Bakr,P radeep and our group recently reported that [Ag 67 S 32 P 8 ] 3 + (Ag 67 ) [35] and [Ag 46 S 24 P 8 ] 2 + (Ag 46 ) [36,37] adopt the FCC space group and bear eight corner phosphine ligands, similarly to the aforementioned Ag 14 , Ag 23 , Ag 38 ,a nd Ag 63 NCs. [31][32][33][34] However, Ag 67 and Ag 46 are exceptionstot he 1D/2D/3D evolution formula, due to their half-cubic [32] growth (Figure 1b vs. 1a).…”

Section: Resultsmentioning

confidence: 99%

“…[22][23][24] The atomic precision with which the structures of these "clustero fc lusters" is understood has allowed the deduction of structure-property correlations. For example, the lowest-energya bsorption peak of Au 13 ,A u 25 ,a nd the rod-likeA u 37 has been found to continuously redshiftw ith increasing size of the NCs. [19] Similarly,f or the aforementioned Au 28 ,A u 36 ,A u 44 ,a nd Au 52 ,t he UV/Vis spectra indicate ad ecreased HOMO-LUMO gap, [22] and femtosecond pump/nanosecond probet ransienta bsorption spectroscopy shows ab roadening of the excited-state absorption with increasingn anocluster size.…”

Section: Introductionmentioning

confidence: 92%

Face‐Centered‐Cubic Ag Nanoclusters: Origins and Consequences of the High Structural Regularity Elucidated by Density Functional Theory Calculations

Chai

et al. 2019

Chemistry A European J

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Face‐centered‐cubic (FCC) silver nanoclusters (NCs) adopting either cubic or half‐cubic growth modes have been recently reported, but the origin of these atomic assembly patterns and how they are achieved, which would inform our understanding of larger FCC silver nanomaterials, are both unknown. In this study, the cubic and half‐cubic growth modes have been unified based on common structural characteristics, and differentiated depending on the starting blocks (cubic vs. half cubic). In both categories, the silver atoms adopt octahedral Ag6, linear AgS2 (in projection drawing), or tetrahedral AgS3P binding modes, and the sulfur atoms adopt T‐shaped SAg3 and orthogonal SAg4 modes. An additional T‐shaped AgS3 mode is oriented on the surface edge in cubic NCs to complete the cubic framework. Density functional theory calculations indicated that the high structural regularity originates from the strong diffusing capacity of the Ag(5d) and S(3p) orbitals, and the angular momentum distribution of the formed superatomic orbitals. The equatorial orientation of μ4‐S or μ4‐Ag determines whether growth stops or continues. In particular, a density‐of‐states analysis indicated that the octahedral silver atoms are chemically more reactive than the silver atoms in the AgS3P motif, regardless of whether the parent NC functions as an electron donor or acceptor.

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Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Cited by 87 publications

References 33 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Insight of the photoluminescence of atomically precise bimetallic nanoclusters with free electrons

Face‐Centered‐Cubic Ag Nanoclusters: Origins and Consequences of the High Structural Regularity Elucidated by Density Functional Theory Calculations

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