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

Chen J, Liu L, Weng L, Lin Y, Liao L, Wang C, Yang J, Wu Z - Sci Rep (2015)

Bottom Line: Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]n nanoclusters (totally 17 novel clusters, n = 4-20).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.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.

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.

No MeSH data available.


PTLC photograph (a) and MALDI-TOF-MS spectra (b) of [Pd(SC2H4Ph)2]n (4 ≤ n ≤ 20).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC4644969&req=5

f1: PTLC photograph (a) and MALDI-TOF-MS spectra (b) of [Pd(SC2H4Ph)2]n (4 ≤ n ≤ 20).

Mentions: The homologous series of phenylethanethiolated Pd clusters were synthesized based on a previous method14. In a typical synthesis, a deoxygenized acetonitrile solution containing Pd(NO3)2•2H2O was mixed with 2 equivalents of 2-phenylethanethiol and 2 equivalents of triethylamine (Note: argon atmosphere is employed to avoid any possible interference from air, but it is not essential for this reaction). After continuously stirred for 5 hrs, the reaction mixture was extracted with CH2Cl2. Then, we thoroughly isolated the components in the crude product via preparative thin layer chromatography (PTLC), which was common in the purification of organic compounds but is rarely used for the isolation of tiara-like metal clusters. Surprisingly and interestingly, the extracted product in our protocol contains at least 17 components as shown by PTLC (see Fig. 1). Of note, at the top of the PTLC plate, there is another band almost indiscernible (marked with an oval, Fig. 1a).


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

Chen J, Liu L, Weng L, Lin Y, Liao L, Wang C, Yang J, Wu Z - Sci Rep (2015)

PTLC photograph (a) and MALDI-TOF-MS spectra (b) of [Pd(SC2H4Ph)2]n (4 ≤ n ≤ 20).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4644969&req=5

f1: PTLC photograph (a) and MALDI-TOF-MS spectra (b) of [Pd(SC2H4Ph)2]n (4 ≤ n ≤ 20).
Mentions: The homologous series of phenylethanethiolated Pd clusters were synthesized based on a previous method14. In a typical synthesis, a deoxygenized acetonitrile solution containing Pd(NO3)2•2H2O was mixed with 2 equivalents of 2-phenylethanethiol and 2 equivalents of triethylamine (Note: argon atmosphere is employed to avoid any possible interference from air, but it is not essential for this reaction). After continuously stirred for 5 hrs, the reaction mixture was extracted with CH2Cl2. Then, we thoroughly isolated the components in the crude product via preparative thin layer chromatography (PTLC), which was common in the purification of organic compounds but is rarely used for the isolation of tiara-like metal clusters. Surprisingly and interestingly, the extracted product in our protocol contains at least 17 components as shown by PTLC (see Fig. 1). Of note, at the top of the PTLC plate, there is another band almost indiscernible (marked with an oval, Fig. 1a).

Bottom Line: Herein, we successfully synthesized, isolated and identified a family of [Pd(SC2H4Ph)2]n nanoclusters (totally 17 novel clusters, n = 4-20).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.

View Article: PubMed Central - PubMed

Affiliation: Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.

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.

No MeSH data available.