Valence self-regulation of sulfur in nanoclusters

Abstract

The valence self-regulation of sulfur from the “−2” valence state in thiols to the “−1” valence state in hydroxylated thiolates has been accomplished using the Pt1Ag28 nanocluster as a platform—the first time that the “−1” valent sulfur has been detected as S−1. Two previously unknown nanoclusters, Pt1Ag28(SR)20 and Pt1Ag28(SR)18(HO-SR)2 (where SR represents 2-adamantanethiol), have been synthesized and characterized—in the latter nanocluster, the presence of hydroxyl induces the valence regulation of two special S atoms from “−2” (in SR) to “−1” valence state in the HO-S(Ag)R. Because of the contrasting nature of the capping ligands in these two nanoclusters [i.e., only SR in Pt1Ag28(SR)20 or both SR- and HO-SR- in Pt1Ag28(SR)18(HO-SR)2], they exhibit differing shell architectures, even though their cores (Pt1Ag12) are in the same icosahedral configuration. Single-crystal x-ray diffraction analysis revealed their 1:1 cocrystallization, and mass spectrometry verified the presence of hydroxyls on Pt1Ag28(SR)18(HO-SR)2.

Trisulfide bond–mediated doxorubicin dimeric prodrug nanoassemblies with high drug loading, high self-assembly stability, and high tumor selectivity

“…Therefore, trisulfide bond (4 e −1 ) has a higher reduction potential than the disulfide bond (2 e −1 ). (iii) The β-sulfur in the trisulfide bond has a higher chemical valence (0) than the sulfur atoms of the disulfide (−1), thereby undergoing reduction more easily ( 33 ).…”

Surface environment complication makes Ag29 nanoclusters more robust and leads to their unique packing in the supracrystal lattice

“…Of note, such a hexagon-like crystallographic packing of Ag 29 -PPh 2 py cluster molecules in the supracrystal lattice was unique, which has yet been detected in other M 29 nanocluster crystals. [44][45][46]48,59,60 For example, for the crystal lattice of Pt 1 Ag 28 -PPh 2 py, the nanocluster molecules were packed with a layered assembly mode from x axis, y axis, or z axis, and no intercluster channel was detected (Fig. S12 †).…”

Cocrystallization of Atomically Precise Nanoclusters

“…In addition, the cocrystallized nanoclusters should have very similar components in terms of both metal composition and ligand type, or the potential metal/ligand-exchange process might result in composition disorder of the cocrystallized system and the further inability to cocrystallize. Since 2018, when nanocluster cocrystallization between (AuAg) 45 and (AuAg) 267 was reported, several efforts have been made to develop more nanocluster cocrystallization cases and investigate cocrystallization-triggered property variations. − Of note, most of these reported cocrystallized nanoclusters were prepared through a one-pot synthetic method, which essentially prevented the metal/ligand exchange-induced disorder.…”

“…The subject of cocrystallization represents one of the most dynamic areas in nanocluster science in very recent years. − Herein, we intend to highlight the relevant advances in studying the cocrystallization of metal nanoclusters. The packing patterns of the cocrystallized nanoclusters, as well as their geometric structures, are discussed case by case in order of the nanocluster size from small to large (Figure ).…”