Understanding the isomerism phenomenon at the nanoscale is a challenging task because of the prerequisites of precise composition and structural information on nanoparticles. Herein, we report the ligand-induced, thermally reversible isomerization between two thiolate-protected 28-gold-atom nanoclusters, i.e. Au28(S-c-C6H11)20 (where -c-C6H11 = cyclohexyl) and Au28(SPh-(t)Bu)20 (where -Ph-(t)Bu = 4-tert-butylphenyl). The intriguing ligand effect in dictating the stability of the two Au28(SR)20 structures is further investigated via dispersion-corrected density functional theory calculations.
The optical properties of metal nanoparticles have attracted wide interest. Recent progress in controlling nanoparticles with atomic precision (often called nanoclusters) provide new opportunities for investigating many fundamental questions, such as the transition from excitonic to plasmonic state, which is a central question in metal nanoparticle research because it provides insights into the origin of surface plasmon resonance (SPR) as well as the formation of metallic bond. However, this question still remains elusive because of the extreme difficulty in preparing atomically precise nanoparticles larger than 2 nm. Here we report the synthesis and optical properties of an atomically precise Au(SR) nanocluster. Femtosecond transient absorption spectroscopic analysis reveals that the Au nanocluster shows a laser power dependence in its excited state lifetime, indicating metallic state of the particle, in contrast with the nonmetallic electronic structure of the Au(SR) nanocluster. Steady-state absorption spectra reveal that the nascent plasmon band of Au at 506 nm shows no peak shift even down to 60 K, consistent with plasmon behavior. The sharp transition from nonmetallic Au to metallic Au is surprising and will stimulate future theoretical work on the transition and many other relevant issues.
Atomic packing controls exciton lifetime Like semiconductors, small metallic clusters can absorb light and create excitons (electron-hole pairs). In ligand-capped gold clusters of 30 to 40 atoms (Au 30 to Au 40 ) that adopt the usual face-centered cubic packing, the lifetime of these excitons is ∼100 nanoseconds. Zhou et al. found that atomic packing and molecular orbital overlap can greatly affect carrier lifetimes. Despite having similar bandgaps to those of face-centered cubic clusters, a hexagonal close-packed Au 30 cluster had a much shorter lifetime (∼1 nanosecond), and a body-centered cubic Au 38 cluster had a lifetime of ∼5 microseconds, which is comparable to bulk silicon. Science , this issue p. 279
We report the synthesis and crystal structure determination of a gold nanocluster with 103 gold atoms protected by 2 sulfidos and 41 thiolates (i.e., 2-naphthalenethiolates, S-Nap), denoted as AuS(S-Nap). The crystallographic analysis reveals that the thiolate ligands on the nanocluster form local tetramers by intracluster interactions of C-H···π and π···π stacking. The herringbone pattern formation via intercluster interactions is also observed, which leads to a linearly connected zigzag pattern in the single crystal. The kernel of the nanocluster is a Marks decahedron of Au, which is the same as the kernel of the previously reported Au(pMBA) (pMBA = -SPh-p-COOH); this is a surprise given the much bulkier naphthalene-based ligand than pMBA, indicating the robustness of the decahedral structure as well as the 58-electron configuration. Despite the same kernel, the surface structure of Au is quite different from that of Au, indicating the major role of ligands in constructing the surface structure. Other implications from Au and Au include (i) both nanoclusters show similar HOMO-LUMO gap energy (i.e., E ≈ 0.45 eV), indicating the kernel is decisive for E while the surface is less critical; and (ii) significant differences are observed in the excited-state lifetimes by transient absorption spectroscopy analysis, revealing the kernel-to-surface relaxation pathway of electron dynamics. Overall, this work demonstrates the ligand-effected modification of the gold-thiolate interface independent of the kernel structure, which in turn allows one to map out the respective roles of kernel and surface in determining the electronic and optical properties of the 58e nanoclusters.
The origin of the near-infrared photoluminescence (PL) from thiolate-protected gold nanoclusters (Au NCs, <2 nm) has long been controversial, and the exact mechanism for the enhancement of quantum yield (QY) in many works remains elusive. Meanwhile, based upon the sole steady-state PL analysis, it is still a major challenge for researchers to map out a definitive relationship between the atomic structure and the PL property and understand how the Au(0) kernel and Au(I)–S surface contribute to the PL of Au NCs. Herein, we provide a paradigm study to address the above critical issues. By using a correlated series of “mono-cuboctahedral kernel” Au NCs and combined analyses of steady-state, temperature-dependence, femtosecond transient absorption, and Stark spectroscopy measurements, we have explicitly mapped out a kernel-origin mechanism and clearly elucidate the surface–structure effect, which establishes a definitive atomic-level structure–emission relationship. A ∼100-fold enhancement of QY is realized via suppression of two effects: (i) the ultrafast kernel relaxation and (ii) the surface vibrations. The new insights into the PL origin, QY enhancement, wavelength tunability, and structure–property relationship constitute a major step toward the fundamental understanding and structural-tailoring-based modulation and enhancement of PL from Au NCs.
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