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Homoleptic Platinum/Silver Superatoms Protected by Dithiolates: Linear Assemblies of Two and Three Centered Icosahedra Isolobal to Ne2 and I3Tzu-Hao Chiu, Jian-Hong Liao, Franck GAM, Isaac Chantrenne, Samia Kahlal, Jean-Yves Saillard, and C.W. Liu J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05000 • Publication Date (Web): 05 Aug 2019 Downloaded from pubs.acs.org on August 6, 2019
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Journal of the American Chemical Society
Homoleptic Platinum/Silver Superatoms Protected by Dithiolates: Linear Assemblies of Two and Three Centered Icosahedra Isolobal to Ne2 and I3Tzu-Hao Chiu,† Jian-Hong Liao,† Franck Gam,‡ Isaac Chantrenne,‡ Samia Kahlal,‡ Jean-Yves Saillard,*‡ C. W. Liu*† Department of Chemistry, National Dong Hwa University, Hualien, Taiwan, R. O. C.
†
‡Univ Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France
Supporting Information Placeholder ABSTRACT: Three bimetallic platinum/silver nanoclusters, PtAg20(dtp)12 (1), Pt2Ag33(dtp)17 (2) and Pt3Ag44(dtp)22 (3) (dtp: dipropyl dithiophosphate), with cluster electron counts of 8, 16, and 22, respectively, were produced via a one-phase co-reduction method. Single-crystal X-ray structures reveal that their inner cores can be visualized as consisting of one, two and three centered icosahedral Pt@Ag12 units, respectively. In (2) and (3), these units are vertex-sharing and assembled linearly. Intriguingly, the 22-electron alloy (3) is isolobal to the linear triiodide anion, I3, and represents the first example of a cluster made of three superatoms whose bonding characteristics are similar to those of a triatomic molecular species.
Mastering the structure-property relationships of atomically precise alloy nanoclusters is exceedingly important due to their multiple potential applications.1 To elucidate alloy structures with atomic resolution, the single-crystal X-ray diffraction technique is the method of choice. Two general synthetic methods are usually applied to design alloy single crystals: galvanic exchange and coreduction.2 Along these lines, a series of structurally precise dichalcogenolate-protected copper and silver superatomic nanoclusters and their alloys have been produced via a template galvanic replacement method.3,4,5 Although highly successful in the construction of group 11 bimetallic nanoclusters (at least for small species), templated galvanic exchange applied to the doping of group 11 clusters with group 10 appears to fail. Therefore, we turned our attention to the co-reduction method, which has been broadly adopted for the fabrication of giant silver-rich alloys protected by ligands such as thiols, phosphines, and alkynyls.2,6 Three brand-new platinum/silver nanoclusters, [PtAg20{S2P(OPr)2}12] (1), [Pt2Ag33{S2P(OPr)2}17] (2), and [Pt3Ag44{S2P(OPr)2}22] (3), were synthesized via this route. The inner cores of all three compounds can be visualized as consisting of centered icosahedral Pt@Ag12 units: one unit for 1 and two and three linearly arranged vertex-sharing units for 2 and 3, respectively. Their cluster electron counts are 8, 16, and 22, respectively. Surprisingly, cluster 3, isolobal to the linear triiodide anion, I3-,7 represents the first example of a superatomic cluster whose bonding characteristics are similar to those of a catenated halide anion. Mixing [NH4][S2P(OnPr)2] and [Ag(CH3CN)4](PF6) in THF followed by the sequential additions of Pt[S2P(OnPr)2]2 and LiBH4
affords a deep brown solution from which three neutral clusters, 1-3, can be separated by chromatography after work-up. The compositions of the three new alloys are accurately determined by mass spectrometry. Two ion peaks (m/z: 5019.2 (5019.1) and 4911.3 (4911.2)) corresponding to [1 + Ag+]+ and [1 + H+]+, respectively, were detected in the positive ESI-MS spectrum of 1 (Figure S1). In the spectra of 2 (Figure S2) and 3 (Figure S3), intense peaks at m/z 3896.5 and 5118.9, which have a half-unit spacing, were attributed to [2 + 2Ag+]2+ (calc. m/z: 3895.6) and [3 + 2Ag+]2+ (calc. m/z: 5119.4), respectively. The solid-state structures of 1-3 were elucidated by the singlecrystal X-ray diffraction technique. The metal framework in 1 contains a Pt@Ag12 centered icosahedral unit, which is further capped by eight silver atoms, leading to a PtAg20 core of idealized C2 symmetry (Figure 1). This unprecedented C2 symmetry is different from that of previously reported isoelectronic clusters that also have a similar octacapped centered icosahedral M21 core (D3,5a C1,5c, 8 and Th5b). The PtAg20 core is stabilized by twelve dithiophosphate (dtp) ligands exhibiting various coordination patterns: tetrametallic tetraconnectivity, trimetallic tetraconnectivity, trimetallic triconnectivity, and bimetallic triconnectivity. It follows that the symmetry of the whole molecule is reduced to C1. The Pt–Ag
Figure 1. (a) The PtAg20 framework of 1 (50% thermal ellipsoids). (b) Overall structure of 1 with the n-propoxy groups omitted for clarity.
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Figure 2. (a) Overall structure of 2 (50% thermal ellipsoids) with the n-propoxy groups omitted for clarity. (b) The Pt2Ag33 framework of 2. Symmetry code: A, 1-x, y, 0.5-z.
Figure 3. (a) The Pt3Ag44 framework of 3 (50% thermal ellipsoids). (b) Overall structure of 3 with the n-propoxy groups omitted for clarity. Symmetry code: A, -x, 2-y, 1-z.
distances in 1 (avg. 2.7601(7) Å) are slightly shorter than the radial Ag–Ag distances in [Ag21{S2P(OiPr)2}12]+ (avg. 2.7789(8) Å).5a This result is in line with the smaller covalent radius of Pt (136 pm) than Ag (145 pm).9 The peripheral Agico–Agico (avg. 2.9022(9) and Agcap–Agico (avg. 2.9022(9) Å) distances are comparable to that in isoelectronic clusters having an M21 core.3,5,8 To our knowledge, only one 8-electron, homoleptic PtAg alloy has been reported so far, namely, [PtAg24(SR)18]2-.10 The inner core of 2 (Figure 2) consists of two Pt@Ag12 centered icosahedra that share a vertex (Ag11), are aligned along a common 5-fold axis and are arranged in a gauche rotational conformation (rotational angle ~ 20°).11 It is worth mentioning that [Pt2Ag23Cl7(PPh3)10], a 16-electron superatom, has a similar Pt2Ag23 vertex-sharing biicosahedral framework,12 which displays an eclipsed rotational conformation. The Pt2Ag23 core of 2 is capped by ten additional Ag atoms (six at the end and four on the sides of the biicosahedral unit) (Figure 2b) and further protected by 17 dtp ligands in three equatorial rows (w and x) and two axial positions (y) (Figure 2a). Each equatorial row has five dtp ligands, and the axial position has one dtp ligand at both ends. The whole molecule has C2 symmetry. The dtp ligands exhibit various coordination patterns: bimetallic biconnectivity, tetrametallic tetraconnectivity, trimetallic tetraconnectivity, and trimetallic triconnectivity. The Pt–Ag distances in 2 (avg. 2.7588(8) Å), as well as the peripheral Agico–Agico (avg. 2.9012(11) Å) and Agcap– Agico (avg. 2.9764(11) Å) distances are similar to those in 1. The Agico–Agico intericosahedral contacts in 2 (avg. 3.0534(12) Å) are longer than those in [Pt2Ag23Cl7(PPh3)10] (avg. 2.949 Å).12 The 31P NMR spectrum of 2 at 293 K displays one sharp peak at 101.1 ppm and two broad bands centered at 95.7 and 104.9 ppm, which can be subsequently resolved into eight peaks at 213 K (Figures S7, S8). The resonance frequency at 101.1 ppm, the line shape of which does not change upon lowering the temperature, can be assigned to the two dtp ligands located at both ends of cluster 2. The five equally intense peaks in the downfield region of 110.1 ~ 103.5 ppm are the chemical shifts of ten dtp ligands, five on each side. The band centered at 95.7 ppm, which can be resolved into three peaks with integration ratios of 1:2:2 at 213 K, can be assigned to the five dtp ligands linking the two PtAg12 units. Thus, the nine peaks corresponding to seventeen dtp ligands strongly suggest that the linear structure of 2 is maintained in solution.
The inner metal core of 3 is composed of three linearly arranged PtAg12 centered icosahedral units that share a common vertex (Ag12 and Ag12A) and are arranged in a gauche rotational conformation with respect to each other (rotational angles ~ 23°). Two related 24-electron species, [Au37(PPh3)10(SC2H4Ph)10X2]+ 13a and [Pt3Ag33(PPh3)12Cl8]+,13b are known. The former cluster has a linear vertex-sharing triicosahedral framework in which the icosahedra are eclipsed with respect to each other. The latter has three vertex-sharing icosahedral PtAg12 motifs arranged in a cyclic manner. The Pt3Ag34 core of 3 is further capped by ten Ag atoms, making it a Pt3Ag44 framework (Figure 3a). As shown in Figure 3b, 22 dtp ligands are connected to the Pt3Ag44 core in four equatorial rows of five ligands (w and x) and two single ligands in axial positions of (y). The ligands adopt tetrametallic tetraconnectivity, trimetallic tetraconnectivity, trimetallic triconnectivity, bimetallic triconnectivity, or bimetallic biconnectivity. The whole molecule is of C1 symmetry. The Pt– Ag distances (avg. 2.7610(4) Å), as well as the peripheral Agico– Agico (avg. 2.9266(6) Å) and Agcap–Agico (avg. 2.9789(6) Å) distances, are similar to those in 1 and 2. The intericosahedral Agico–Agico (avg. 3.0420(6) Å) contacts are close to those in 2. Within the framework of the superatom concept,14 1 is an 8electron superatom with a 1S2 1P6 noble gas-like jellium15 electron configuration. This configuration is confirmed by DFT calculations16 on a simplified model of 1, [PtAg20(S2PH2)12] (1’), which shows an electronic structure related to that of the previously reported isoelectronic M@Ag20 (M = Ag, Au) species.5 In other words, 1 can be formally described as an 8electron [PtAg12]4+ superatomic core passivated by eight Ag+ and twelve dtp- ions. The strong preference for Pt occupying the icosahedron center (by more than 28 kcal/mol) is related to its electronegativity being larger than that of Ag.5b-d 2 has 16 electrons, indicating that, similar to other isoelectronic vertexsharing biicosahedral clusters,17 it is made of two “noninteracting” 8-electron vertex-sharing icosahedral superatoms, thus making it isolobal to Ne2.17c,d This finding is confirmed by DFT calculations on a simplified model of 2, [Pt2Ag33(S2PH2)17] (2’), which allows 2 to be described formally as a 16-electron [Pt2Ag23]7+ superatomic assembly passivated by 10 Ag+ and 17 dtp- ions. Whereas one would extrapolate a count of 3 x 8 = 24 electrons for three “noninteracting” vertex-sharing icosahedra, astonishingly, the electron count of 3 is 22. This count indicates interactions between the superatomic orbitals associated with each individual centered icosahedron. In fact, assuming the isolobal
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Journal of the American Chemical Society
ag au
1σu*
ag
a2u*
1σu*
au ag ag
LUMO LUMO
LUMO a2u*
0.53eV 2πu*
au
1.63eV
HOMO HOMO
HOMO
e1u*
1.03eV
e1g
0.87eV
1πg
elongated by 0.10 Å and 0.13 Å on average, thus rendering the inter-superatom interactions nonsignificant. The lowest-energy absorption peak displays a redshift from 412 nm in 1 to 710 nm in 2 and to 956 nm in 3 (Figure S13), which is reproduced in the TD-DFT-simulated spectra (Figure S14). These absorption bands correspond to HOMO-LUMO transitions, which decrease in energy with increasing assembly building units. The emission spectra of 1 and 2 at 77 K are consistent with their absorption behavior (Figure S21). Unfortunately, 3 does not luminesce at the wavelengths examined in this work. In conclusion, we report herein three new platinum/silver superatomic alloys, which are assembled through a Pt@Ag12 icosahedral building unit. While the cluster electron counts of 8 and 16 for alloys 1 and 2, respectively, are not unusual, cluster 3, a linear assembly of three vertex-sharing PtAg12 units with 22 electrons, is the first example of a superatom whose electronic structure is isolobal to the triiodide ion. The intericosahedral bonding interactions presented here will open a research frontier in superatomic alloys, and efforts toward the isolation of 24electron species, namely, [Pt3Ag44{S2P(OPr)2}22]2- and [Pt1Ag46{S2P(OPr)2}22], are ongoing.
ASSOCIATED CONTENT e1u*
2πu* ag au
HOMO-1
au
3σg
a1g
ag
a1g
ag au
Supporting Information The Supporting Information is available free of charge on the ACS Publication website at DOI: 10.1021/jacs.xxxxxxx. Synthetic details; ESI-MS, NMR, UV-vis, XPS spectra; computational details (PDF)
e1g
Crystallographic information files for 1-3, also available from CCDC under deposition numbers 1901406 (1), 1901407 (2), and 1901408 (3) (CIF)
1πg
au HOMO-2
AUTHOR INFORMATION
3σg
[Pt3Ag44(S2PH2)22] (Ci)
[I3]- (D∞h)
[Pt3Ag34]12+ (D5d)
Figure 4. Left side: Kohn-Sham orbital diagram of 3’. Right side: Kohn-Sham orbital diagrams of I3- and of an idealized 22-electron [Pt3Ag34]12+ core. The diagram of the [Pt3Ag34]12+ core of 3 (or 3’) is approximately the same, but with (minor) additional orbital mixing/splitting due to lower symmetry. analogy of a 7-valence-electron iodine atom (5s2 5p5) with a 7electron icosahedral superatom (1S2 1P5), 3 can be considered an isolobal analog of the linear hypervalent 22-electron triiodide (I3-) anion. DFT calculations fully confirm this assumption, as exemplified by the Kohn-Sham MO diagram (Figure 4, left) of a simplified model of 3, [Pt3Ag44(S2PH2)22] (3’), which exhibits a LUMO of a similar shape and phase relationship as that of I3-. The occupied orbitals can be indexed as equivalent to those of I3-. For example, the HOMO-1 and HOMO-2 are the counterparts of the 2u* HOMOs of I3-. The orbital analogy is even more striking when comparing the orbitals of a 22-electron triicosahedral [Pt3Ag34]12+ core with those of triiodide (Figure 4, right). Analysis of the electronic structure of 3’ allows it to be described as a 22electron [Pt3Ag34]12+ assembly passivated by 10 Ag+ and 22 dtpions. Its HOMO-LUMO gap (0.87 eV) is lower than that of 2’, in agreement with moderate intericosahedral bonding interactions. The LUMO lies in an energy gap 0.53 eV below the LUMO+1, suggesting that a count of 24 electrons, as in the case of [Au37(PPh3)10(SC2H4Ph)10X2]+,13 is also possible. Calculations on [3’]2- found a HOMO-LUMO gap of 0.74 eV with no significant HOMO-HOMO-1 gap (Figure S20). The molecular structure indicates weaker intericosahedral contacts in [3’]2- than in 3’, with the corresponding Pt-Ag and Agico1-Agico2 distances being
Corresponding Author *
[email protected] *
[email protected] ORCID C. W. Liu.: 0000-0003-0801-6499 Jean-Yves Saillard: 0000-0003-4469-7922 Jian-Hong Liao: 0000-0002-7947-1790
Notes The authors declare no competing financial interest.
ACKNOWLEDGMENT This work was supported by Ministry of Science and Technology in Taiwan (MOST 106‐2113‐M‐259‐010; 108-2923-M-259-001), the ANR-MOST program (project Nanoalloys), and the GENCI computer resource center (grant A0030807367). We greatly thank professor Yuan-Chang Chen of Fu Jen Catholic University for recording UV-vis-NIR and emission spectra.
REFERENCES (1)
(a) Jin, R.; Zhen, C.; Zhou, M.; Chen, Y. Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities. Chem. Rev. 2016, 116, 10346-10413. (b) Chakraborty, I.; Pradeep, T. Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles. Chem. Rev. 2017, 117, 8208-8271. (c) Jin, R.; Pei, Y.; Tsukuda, T. Controlling Nanoparticles with Atomic Precision. Acc. Chem. Res. 2019, 52, 1. (d) Kang, X.; Zhu, M. Tailoring the photoluminescence of atomically precise nanoclusters, Chem. Soc. Rev. 2019, 48, 24222457.
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(3)
(4)
(5)
(6)
(a) Ghosh, A.; Mohammed, O. F.; Bakr, O. M. Atomic-Level Doping of Metal Clusters. Acc. Chem. Res. 2018, 51, 3094-3103. (b) Wang, S.; Li, Q.; Kang, X.; Zhu, M. Customizing the Structure, Composition, and Properties of Alloy Nanoclusters by Metal Exchange. Acc. Chem. Res. 2018, 51, 2784-2792. (c) Hossain, S.; Niihori, Y.; Nair, L. V.; Kumar, B.; Kurashige, W.; Negishi, Y. Alloy Clusters: Precise Synthesis and Mixing Effects. Acc. Chem. Res. 2018, 51, 3114-3124. (d) Gan, Z.; Xia, N.; Wu, Z. Discovery, Mechanism, and Application of Antigalvanic Reaction. Acc. Chem. Res. 2018, 51, 2774-2783. (e) Bhattarai, B.; Zaker, Y.; Atnagulov, A.; Yoon, B.; Landman, U.; Bigioni, T. P. Chemistry and Structure of Silver Molecular Nanoparticles. Acc. Chem. Res. 2018, 51, 31043113. (f) Liu, J.-Y.; Alkan, F.; Wang, Z.; Zhang, Z.-Y.; Kurmoo, M.; Yan, Z.; Zhao, Q.-Q.; Aikens, C. M.; Tung, C.-H.; Sun, D. Different Silver Nanoparticles in One Crystal: Ag210(iPrPhS)71(Ph3P)5Cl and Ag211(iPrPhS)71(Ph3P)6Cl. Angew. Chem. Int. Ed. 2019, 58, 195-199. (g) Liu, J.-W.; Wang, Z.; Chai, Y.-M.’ Kurmoo, M.; Zhao, Q.-Q.; Wang, X.-P.; Tung, C.-H.; Sun, D. Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters. Angew. Chem. Int. Ed. 2019, 58, 6276-6279. (h) Wang, Z.; Senanayake, R.; Aikens, C. M.; Chen, W.M.; Tung, C.-H.; Sun, D. Gold-doped silver nanocluster [Au3Ag38(SCH2Ph)24X5]2− (X = Cl or Br). Nanoscale, 2016, 8, 18905-18911. (i) Zhang. S.-S.; Alkan F.; Su, H.-F.; Aikens, C. M.; Tung, C.-H, Sun, D. [Ag48(C≡CtBu)20(CrO4)7]: An Atomically Precise Silver Nanocluster Co-protected by Inorganic and Organic Ligands. J. Am. Chem. Soc. 2019, 141, 4460-4467. Sharma, S.; Chakrahari, K. K.; Saillard, J.-Y.; Liu, C. W. Structurally Precise Dichalcogenolate-Protected Copper and Silver Superatomic Nanoclusters and Their Alloys. Acc. Chem. Res. 2018, 51, 2475-2483. (a) Silalahi, R. P. B.; Chakrahari, K. K.; Liao, J.-H.; Kahlal, S.; Liu, Y.-C.; Chiang, M.-H.; Saillard, J.-Y.; Liu, C. W. Synthesis of TwoElectron Bimetallic Cu-Ag and Cu-Au Clusters by using [Cu13(S2CNnBu2)6(C≡CPh)4]+ as a Template. Chem. Asian. J. 2018, 13, 500-504. (b) Chakrahari, K. K.; Liao, J.-H.; Kahlal, S.; Liu, Y.C.; Chiang, M.-H.; Saillard, J.-Y.; Liu, C. W. [Cu13{S2CNnBu2}6(acetylide)4]+: A Two-Electron Superatom. Angew. Chem. Int. Ed. 2016, 55, 14704-14708. (a) Dhayal, R. S.; Liao, J.-H.; Liu, Y.-C.; Chiang, M.-H.; Kahlal, S.; Saillard, J.-Y.; Liu, C. W. [Ag21{S2P(OiPr)2}12]+: An Eight-Electron Superatom. Angew. Chem. Int. Ed. 2015, 54, 3702-3706. (b) Chang, W.-T.; Lee, P.-Y.; Liao, J.-H.; Chakrahari, K. K.; Kahlal, S.; Liu, Y.C.; Chiang, M.-H.; Saillard, J.-Y.; Liu, C. W. Eight-Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Se-Donor Ligands. Angew. Chem. Int. Ed. 2017, 56, 10178-10182. (c) Liao, J.H.; Kahlal, S.; Liu, Y.-C.; Chiang, M.-H.; Saillard, J.-Y.; Liu, C. W. Identification of an Eight-Electron Superatomic Cluster and Its Alloy in One Co-crystal Structure. J. Clust. Sci. 2018, 29, 827-835. (d) Lin, Y.-R.; Kishore, P. V. V. N.; Liao, J.-H.; Kahlal, S. Liu, Y.-C.; Chiang, M.-H.; Saillard, J.-Y.; Liu, C. W. Synthesis, structural characterization and transformation of an eight-electron superatomic alloy, [Au@Ag19{S2P(OPr)2}12]. Nanoscale 2018, 10, 6855-6860. (a) Yan, J.; Teo, B. K.; Zheng, N. Surface Chemistry of Atomically Precise Coinage-Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis. Acc. Chem. Res. 2018, 51, 30843093.(b) Chen, T.; Yang, S.; Chai, J.; Song, Y.; Fan, J.; Rao. B.; Sheng, H.; Yu, H.; Zhu, M. Crystallization-induced emission enhancement: A novel fluorescent Au-Ag bimetallic nanocluster with precise atomic structure. Sci Adv. 2017, 3, e1700956. (c) Kang, X.; Zhou, M.; Wang, S.; Sun, G.; Zhu, M.; Jin, R. The tetrahedral structure and luminescence properties of Bi-metallic Pt1Ag28(SR)18(PPh3)4 nanocluster. Chem. Sci. 2017, 8, 2581-2587.(d) He, L.; Yuan, J.; Xia, N.; Liao, L.; Liu, X.; Gan, Z.; Wang, C.; Yang, J.; Wu, Z. Kernel Tuning and Nonuniform Influence on Optical and Electrochemical Gaps of Bimetal Nanoclusters. J. Am. Chem. Soc. 2018, 140, 3487-3490. (e) Wang, S.; Jin, S.; Yang, S.; Chen, S.; Song Y.; Zhang, J.; Zhu, M. Total structure determination
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(15)
(16) (17)
of surface doping [Ag46Au24(SR)32](BPh4)2 nanocluster and its structure-related catalytic property. Sci. Adv. 2015, 1, e1500441. Landrum, G. A.; Goldberg, N.; Hoffmann, R. Bonding in the trihalides (X3-), mixed trihalides (X2Y-) and hydrogen bihalides (X2H-). The connection between hypervalent, electron-rich threecenter, donor–acceptor and strong hydrogen bonding. J. Chem. Soc. Dalton Trans. 1997, 3605-3613. Chang, W.-T.; Sharma, S.; Liao, J.-H.; Kahlal, S.; Liu, Y.-C.; Chiang. M.-H.; Saillard, J.-Y.; Liu, C. W. Hereroatom-Doping Increases Cluster Nuclearity: From an [Ag20] to an [Au3Ag18] Core. Chem. Eur. J. 2018, 24, 14352-14357. Cordero, B.; Gómez, V.; Platero-Prats, A. E.; Revés, M.; Echeverría, J.; Cremades, E.; Barragán, F.; Alvarez, S. Covalent radii revisited. Dalton. Trans. 2008, 2832-2838. Yan, J.; Su, H.; Yang, H.; Malola, S.; Lin, S.; Häkkinen, H.; Zheng, N. Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18]2– (M = Pd, Pt) Clusters. J. Am. Chem. Soc. 2015, 137, 11880-11883. Teo, B. K.; Zhang, H. Polyicosahedricity: icosahedron to icosahedron of icosahedra growth pathway for bimetallic (Au-Ag) and trimetallic (Au- Ag-M; M = Pt, Pd, Ni) supraclusters; synthetic strategies, site preference, and stereochemical principles. Coord. Chem. Rev. 1995, 143, 611-636. Bootharaju, M. S.; Kozlov, S. M.; Cao, Z.; Harb, M.; Maity, N.; Shkurenko, A.; Parida, M. R.; Hedhili, M. N.; Eddaoudi, M.; Mohammed, O. F.; Bakr, O. M.; Cavallo, L.; Basset. J.-M. DopingInduced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters. J. Am. Chem. Soc. 2017, 139, 1053-1056. (a) Jin, R.; Liu, C.; Zhao, S.; Das, A.; Xing, H.; Gayathri, C.; Xing, Y.; Rosi, N. L.; Gil, R. R.; Jin, R. Tri-icosahedral Gold Nanocluster [Au37(PPh3)10(SC2H4Ph)10X2]+: Linear Assembly of Icosahedral Building Blocks. ACS Nano 2015, 9, 8530-8536. (b) Yang, S.; Chai, J.; Lv, Y.; Chen, T.; Wang, S.; Yu, H.; Zhu, M. Cyclic Pt3Ag33 and Pt3Au12Ag21 nanoclusters with M13 icosahedra as building-blocks. Chem. Commun. 2018, 54, 12077-12080. (a) Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Whetten, R. L.; Grönbeck, H.; Häkkinen, H. A unified view of ligand-protected gold clusters as superatom complexes. Proc. Natl. Acad. Sci. USA 2008, 105, 91579162. (b) Häkkinen, H. Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts. Chem. Soc. Rev. 2008, 37, 1847-1859. (a) Lin, Z.; Slee, T.; Mingos, D. M. P.; A structural jellium model of cluster electronic structure. Chem. Phys. 1990, 142, 321-334. (b) Mingos, D. M. P. Structural and Electronic Paradigms in Cluster Chemistry; Springer; Berlin, Heidelberg, 1997. (c) Teo, B. K.; Yang, S.-Y. Jelliumatic Shell Model. J. Clust. Sci. 2015, 26, 1923-1941. (d) Khanna, S. N.; Jena, P. Atomic clusters: Building blocks for a class of solids Phys. Rev. B. 1995, 51, 13705-13716. See SI for computational details. (a) Shichibu, Y.; Negishi, Y.; Watanabe, T.; Chaki, N. K.; Kawaguchi, H.; Tsukuda, T. Biicosahedral Gold Clusters [Au25(PPh3)10(SCnH2n+1)5Cl2]2+ (n = 2−18): A Stepping Stone to Cluster-Assembled Materials. J. Phys. Chem. C 2007, 111, 78457847. (b) Nobusada, K.; Iwasa, T. Oligomeric Gold Clusters with Vertex-Sharing Bi- and Triicosahedral Structures. J. Phys. Chem. C 2007, 111, 14279-14282. (c) Mingos, D. M. P. Structural and bonding patterns in gold clusters. Dalton. Trans. 2015, 44, 66806695. (d) Jin, S.; Zou, X.; Xiong, L.; Du, W.; Wang, S.; Pei, Y.; Zhu, M. Bonding of Two 8-Electron Superatom Clusters. Angew. Chem. Int. Ed. 2018, 57, 16768-16772. (e) Kim, M.; Tang, Q.; Narendra Kumar, A. V.; Kwak, K.; Choi, W.; Jiang, D.-e., Lee, D. DopantDependent Electronic Structures Observed for M2Au36(SC6H13)24 Clusters (M = Pt, Pd). J. Phys. Chem. Lett. 2018 9, 982-989.
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