Synthesis and Properties Evolution of a Family of Tiara-like Phenylethanethiolated Palladium Nanoclusters

Abstract

Tiara-like thiolated group 10 transition metal (Ni, Pd, Pt) nanoclusters have attracted extensive interest due to their fundamental scientific significance and potential application in a number of fields. However, the properties (e.g. the absorption) evolution with the ring size’s increase was not investigated so far to our best knowledge, due to the challenge of obtaining a series of nanocluster analogues. Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]n nanoclusters (totally 17 novel clusters, n = 4–20). Their structures were determined to be tiara-like by single crystal X-ray crystallography together with theoretical calculation; their formation mechanism was proposed to be a substitution—polycondensation—ring-closure process based on experimental observations. All of these clusters are rather robust (anti-reductive and anti-oxidative) owing to their tiara-like structures with large HOMO-LUMO gaps. Finally, the optical and electrochemical evolution with the increase of ring size was investigated, and it is found that both optical and electrochemical gaps have a “turning point” at a size corresponding to n = 8 for [Pd(SR)2]n nanoclusters.

High Refractive Index Inverse Vulcanized Polymers for Organic Photonic Crystals

“…Figure 1b shows the real (n) and imaginary (k) part of the complex refractive index (n + ik) of the polymer with the intermediate 70 wt% sulfur concentration (n, red line; k, black line). The extinction coefficient was almost structureless, and only two weak features at 230 and 300 nm could be detected and assigned to the sulfur chains, with an absorption tail extending to the near infrared [50]. The real part of the refractive index showed a relevant value out of resonance (1.77 at 2500 nm) and a normal dispersion up to the broad peak at 372 nm (n = 1.88).…”

Platinum clusters with precise numbers of atoms for preparative-scale catalysis

“…As the precursors of such ultrasmall platinum subnanoparticles, platinum thiolates are currently being investigated because reductive metal-sulfur bond cleavage might lead to the formation of bare metal clusters. The thiolates can form tiara-like cyclic complexes stable enough for isolation 22 – 27 . In principle, such tiara-like complexes are available with atomicities of 4 and higher 28 .…”

Deepening the Understanding of Thiolate-Protected Metal Clusters Using High-Performance Liquid Chromatography

“…682 Pd belongs to group 10 of the periodic table and its bonding nature with thiolate differs from those of Au and Ag, which both belong to group 11. 544 It is presumed that for this reason, simple substitution between Pd and Au is unlikely to occur; therefore, substitution by Pd was limited to low numbers.…”