Reversible isomerization of metal nanoclusters induced by intermolecular interaction

•Structural tuning of inorganic nanoparticles is realized in an indirect manner•Intermolecular interaction determines the core structure nanoparticles•Reversible isomerization metal nanoclusters solution•Rigid surface-adsorption layer molecules triggers process The atomic-packing mode inner greatly influences their physical and chemical properties. Current strategies for customizing usually involve direct with core. Here, we show that interaction, i.e., intermolecular between surface ligands adsorbed molecules, can be used to reversibly tailor atomic packing ultrasmall (i.e., nanoclusters), thus realizing reversible solution. Reversible two isomers [Au25(p-MBA)18]? achieved through coupling/decoupling CH???? p-MBA CTA+ ions (p-MBA denote para-mercaptobenzoic acid cetyltrimethylammonium, respectively). This study provides a new way customize without changing ligands. Most are directly terminated (and stabilized) by protecting ligands, which could affect physical/chemical properties cores. interactions also nanoparticles. Through cationic surfactants (cetyltrimethylammonium cations, CTA+) anionic (para-mercaptobenzoic acid, p-MBA) aqueous phase, have transformation nanoclusters. interconversion shows characteristics nanocluster process. topologically connected via simple rotation gold breaking any Au-S bonds at metal-ligand interface. cations would interact stabilize more open ligand shell isomer forward IntroductionInorganic much larger area and, therefore, greater energy than bulky counterparts. As result, surface-protecting mostly organic crucial structural component nanoparticles, terminate states them nanoscale size.1Yin Y. Alivisatos A.P. Colloidal nanocrystal synthesis organic-inorganic interface.Nature. 2005; 437: 664-670Crossref PubMed Scopus (2852) Google Scholar,2Xia Y.N. Xiong Y.J. Lim B. Skrabalak S.E. 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Chemically clusters.Science. 2019; 363: 731-735Crossref (40) ligand-protected mainly depends on adjustment exchange. exchange pseudo-isomers same number but pseudo-isomerization process, 1).17Chen C. Tang Higaki Das Jiang D.E. Rosi N.L. Jin Isomerism Au28(SR)20 stable structures.J. 138: 1482-1485Crossref (201) Scholar,18Kang Pei Z.H. S.X. Wei S.Q. face-centered cubic icosahedral isomers.Chem. Sci. 8685-8693Crossref However, makes nontrivial (if not impossible) decouple cluster properties.Several reported, such Au38 Au23 nanoclusters;19Tian S.B. Y.Z. M.B. Yuan J.Y. Yang J.L. revealed X-ray crystallography.Nat. 8667Crossref (196) Scholar,20Guan Z.J. Hu Wen Z.R. Lin Y.M. Q.M. alkynyl-protected nanoclusters.J. 2020; 142: 2995-3001Crossref (60) however, only thermodynamically preferred possible. reverse prohibited, indicates reconstruction most likely occur breaking/regenerating rather displacive reconfiguration.16Williamson Au13Ag12 spontaneously interconvert specific temperatures,21Qin Zhang J.W. Wan C.Q. Abroshan G. isomeric rotary nanomotors.Nat. 11: 6019Crossref (31) involves bonds, driving force level still unknown. Another was observed Au28 binding motifs (Au(I)-SR motifs; SR denotes thiolate ligand) involving core-motif interface triggered solvent environment, while keeping identical.22Xia N. Liao L.W. W.H. Deng H.T. oscillation nanoparticles.J. 12140-12145Crossref (25) Au144 identified aberration-corrected transmission electron microscopy (TEM),23Takahata R. Yamazoe Maehara Yamazaki K. Takano Kurashige Gohara Tsukuda Electron microscopic observation Au13 Core Au25(SePh)18 cores Au144(SC2H4Ph)60.J. Phys. 124: 6907-6912Crossref (11) considered random under electron-beam irradiation. More recently, novel extremely well-studied Au25(SR)18? predicted24Matus M.F. Malola Kinder Bonilla E.K. Barngrover B.M. Aikens C.M. A topological nanocluster.Chem. 56: 8087-8090Crossref gas phase,25Kalenius E. Matus Kazan Bürgi Experimental confirmation ubiquitous Au25(SR)18 phase.J. 143: 1273-1277Crossref (12) whose driven cluster-cluster collisions. Based density theory (DFT) calculations, plausible mechanism proposed collective core-ligand believed responsible racemization enantiomers) chiral Au38(PET)24 (PET 2-phenylethylthiolate).26Knoppe Dolamic Racemization nanoparticle evidences flexibility gold-thiolate interface.J. 2012; 134: 13114-13120Crossref (93) Scholar,27Malola Chiral inversion Bond.J. 141: 6006-6012Crossref (50) ScholarThe processes discussed above spontaneous induced sufficient internal kinetic solution collisions phase. up now, there no chemically controllable induce interaction—the molecules—can “genuine” (Scheme By coupling (cetyltrimethylammonium) deprotonated common acid) obtained [Au25(p-MBA)18]?. Moreover, decoupling ions. reaction kinetics typical activation energies 1.16 1.17 eV, respectively. rationalized DFT calculations models based analysis optical absorption spectra powder diffraction patterns. comparison experimental theoretical data occurs similar long-known 28Heaven M.W. Dass White P.S. Holt K.M. Murray R.W. [N(C8H17)4] [Au25(SCH2CH2Ph)18].J. 2008; 130: 3754-3755Crossref (1283) Scholar,29Zhu Hollander F.J. Schatz G.C. Correlating thiol-protected Au25 properties.J. 5883-5885Crossref (1742) recently observed25Kalenius Au25(PET)18?/+ Combining dynamics (MD) simulations, gain insights isomerization, reveal key On one hand, form highly rigidified double-layer surfaces other mediate phenyl ring ligand, conducive ligand-shell surface. method extended using organosoluble construct structure. our work paves controlling weak interactions, making possible expand adjustability applications.Results discussionIsomer (Au25)R (Au25)GIn experiment, (reddish brown denoted (Au25)R) first synthesized carbon monoxide (CO)-reduction (see supplemental procedures).30Luo Z.T. Nachammai V. Yan Leong D.T. Xie J.P. Toward understanding mechanism: tracing all intermediate reduction Au(I)-thiolate complexes evolution 10577-10580Crossref (260) After that, were introduced adding CTAB change charge We zeta potential monitor state during (Figure 1A). initial ?45 mV, indicating alkaline conditions, negatively charged originated carboxylic groups. introduction CTAB, changed +43 structure, balanced first-layer layer) further transferred positive second-layer 1B). According nuclear magnetic resonance (NMR) spectra, contains 12 per (please refer procedures; Figures S1 S2). widely CTA+-nanoparticle system,31Gao J.X. Bender Murphy Dependence nanorod aspect ratio directing surfactant solution.Langmuir. 19: 9065-9070Crossref (577) Scholar,32Murphy Sau T.K. Gole A.M. Orendorff Gao Gou Hunyadi Anisotropic assembly, applications.J. 109: 13857-13870Crossref (2677) observations experiments confirmed individual if amount S3).Figure 1Reversible nanoclustersShow full caption(A) corresponding potentials Insets digital images solutions stages.(B) Schematic illustration surface.(C) UV-vis before after transformation.(D) ESI-MS (Au25)R. All main peaks mass assigned combining Na+ (blue rectangle), each perfect fitting isotopic pattern (red rectangle, red line).(E) (Au25)G. numbers line). Please see Figure S8 assignments peaks.View Large Image ViewerDownload Hi-res image Download (PPT)After adsorption, color gradually reddish dark green (about 2 weeks 25°C) distinctly indicate 1C). Transmission (TEM) suggests products diameter nm) S4). high purity precursor electrospray-ionization spectrometry (ESI-MS) NMR (Figures 1D S5), point known [Au25(p-MBA)18]?.28Heaven then determine newly formed species, identical result precursor, ([Au25]R, 1E). fragmentation given tandem different, although both [Au25(p-MBA)18]?, should inherently S6 S7). hereinafter referred (Au25)G, solution.Reverse (Au25)G (Au25)R(Au25)G precipitated ethanol redissolved methanol. negative (?35 mV) 1A), behavior solvents probably due better solvation methanol water, leads dissociation instead ions, shifted back 4 h temperature), its conversion realized. solid S9), independent transfer very entire cycle isomerization) easily repeated procedures S10).Reaction isomerizationThe fulfill transition first-order observable intermediates.16Williamson studied 2A 2B characteristic Both fitted perfectly kinetics: (Au25)R/G% = e?kt, where percentage starting k rate constant t time. Arrhenius prefactor calibrated temperatures equation 2C S11–S20). calculated prefactors 1.19 × 1014 s?1 6.82 1015 these reactions, correspond vibrational frequency across intermediates. lifetime order 10?14 s procedures), isosbestic points 2A, 2B, S11–S20) support conclusion.Figure 2Reaction processesShow Time-course 60°C kinetics.(B) 30°C kinetics.(C) plot (dash lines). Ea, energy; A, prefactor.View (PPT)The respectively, close (~1 eV).16Williamson barrier small enough reconfiguration coordination bonds), giving Interestingly, barriers case Ea 1.22 3.32 s?1).26Knoppe proven (energy barrier: 1–1.5 eV).27Malola ScholarDFT proposal isomerRecently, rule, predicted low-barrier (0.6 eV) phase.24Matus Scholar,25Kalenius investigated earlier computations characterize electronic ground linear-response (LR) time-dependent (TD) analyze (with p-MBA). performed GPAW software technical details LR-TDDFT/DFT information).33Enkovaara