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Strong chiroptical activity in Au25 clusters protected by mixed ligands of chiral phosphine and achiral thiolate

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Abstract

We report the successful synthesis of a chiroptically active Au25 cluster protected by mixed ligands of chiral bidentate S-BINAP and achiral dodecanethiol (DDT), which can be formulated as [Au25(S-BINAP)4(DDT)5X4] (X = Cl or Br). The UV-vis absorption spectral pattern is similar to that of the well-known bi-icosahedral cluster [Au25(PPh3)10(SR)5X2]2+, so the obtained cluster should also have a similar bi-icosahedral structure assembled from two vertex-sharing icosahedral Au13 units. With a closer inspection of the optical absorption, interestingly, the lowest-energy peak is red-shifted as compared to that of [Au25(PPh3)10(SR)5X2]2+. Quantum chemical calculations for model bi-icosahedral Au25 structures suggest the reason of the red shift. On the other hand, the obtained Au25 cluster exhibits a weak CD signature in the lowest-energy transition region, whereas higher-energy transitions have very large chiroptical responses with a maximum g-factor of 1.7 × 10−3. The calculations also give implications for the origin of the CD response in the Au25 cluster. We then believe that bi-icosahedral Au25 clusters with chirality will be a good prototype for understanding the influence of constituent Au13 units on the chiroptical activity of their assembling structures.

Graphical abstract: Strong chiroptical activity in Au25 clusters protected by mixed ligands of chiral phosphine and achiral thiolate

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Supplementary files

Article information


Submitted
10 May 2020
Accepted
23 Jun 2020
First published
23 Jun 2020

Phys. Chem. Chem. Phys., 2020, Advance Article
Article type
Paper

Strong chiroptical activity in Au25 clusters protected by mixed ligands of chiral phosphine and achiral thiolate

T. Nashimoto and H. Yao, Phys. Chem. Chem. Phys., 2020, Advance Article , DOI: 10.1039/D0CP02543G

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