Superatoms. Группа авторов

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Superatoms - Группа авторов


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target="_blank" rel="nofollow" href="#ulink_cd0f40b0-42da-5400-a995-77ab41ec4fcf">Figure 2.10 Q(M) versus η (X = F, Cl, Br, I) for (a) MX (M = Al11–Al15, Al, halogen atoms) and (b) MX2 (M = Al11–Al15, Al, Si, alkaline earth atoms). The data of Al11 through Al15 basically coincide without revealing any exceptions for Al13 or Al14.

      Source: Han and Jung [33]. © American Chemical Society.

Schematic illustration of initial crystal structure for (a) body-centered-cubic (bcc), (b) rock salt (rs), and (c) zinc-blende (zb) phases of (CH3)4N+Al13- bulk. (d) Optimized structures of (CH3)4N+Al13- show the coalescence of Al13 clusters when forming a bulk material.

      Source: Huang [36]. © American Chemical Society.

      On the contrary, jellium shell closure rule has been effectively used to explain the stability of ligated metal clusters, particularly ligated Cu, Ag, and Au clusters. As the number of atoms in the metal core as well as the number and type of ligands can be varied independently, one is gifted with considerable flexibility to design ligated metal clusters as superatoms. Consider, for example a metal core consisting of NC number of core atoms and NS number of surface atoms. The surface atoms are the ones that bind to the ligands forming either an ionic or a covalent bond. If the number of valence electrons in the core atoms correspond to shell closure, it is likely that such a cluster can gain unusual stability. Hakkinen and coworkers [37, 38] used this approach to explain the unusual stability of some ligated Al and Au clusters. For example, the unusual stability of Al50Cp*12 can be explained by realizing that 12 Cp* ligands withdraw 12 electrons from the Al50 core, thus leaving 50 × 3 − 12 = 138 electrons. This is just enough electrons to close the 1I superatom jellium shell. Similarly, the authors showed that ligand‐protected Au clusters, satisfying electron shell closure at 8, 34, and 58, can indeed be synthesized.

      2.2.2 Octet Rule

ne Examples
2 Ag14(SR)12(PR)8, Ag16(SR)14(dppe)4, {Au34[Fe(CO)3]6 [Fe(CO)4]8}8−
8 Au11X3(PR3)7, [Au13Cl2(PR3)10]3+, [Au25(PET)18] , Au28(SR)20, Al4(C5Me5)4, Al4[SiC(CH3)3]4, [Au13Cu2(PR)6(SPy)6]+, [Au13Cu4(PR2Py)4(SR)8]+, [Au13Cu8(SPy)12]+, [Au11(dpdp)6]3+, {Ag21[S2P(O/Pr)2]12}+
18 [Ag44(SR)30]−4, [Ag44(SR)30]−4, [Au12Ag32(SR)30]−4, [Au12+nCu32(SR)30+n]−4 (n = 0, 2, 4, 6), Au24Ag20(SR)4(C2Ph)20Cl2
34 [Au39(PR3)14Cl6], Au68(SR)34, [Au67(SR)35] −2, Au39Cl6(PH3)14
40 {Ge9[Si(SiMe3)3]3}, SiAl14(C5Me5)6
58 Au102(p‐MBA)44, Au102(SMe)44, {GaGa11[GaN(SiMe3)2]11}
138 Al50(C5Me5)12
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