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Light-Activated Intercluster Conversion of an Atomically Precise Silver Nanocluster
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SYSNO ASEP 0547275 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Light-Activated Intercluster Conversion of an Atomically Precise Silver Nanocluster Author(s) Jana, A. D. (IN)
Jash, M. (IN)
Poonia, A. K. (IN)
Paramasivam, G. (IN)
Islam, M. R. (IN)
Chakraborty, P. (IN)
Antharjanam, S. (IN)
Macháček, Jan (UACH-T) RID, ORCID, SAI
Ghosh, S. (IN)
Adarsh, K. N. V. D. (IN)
Baše, Tomáš (UACH-T) RID, SAI, ORCID
Pradeep, T. (IN)Number of authors 12 Source Title ACS Nano. - : American Chemical Society - ISSN 1936-0851
Roč. 15, č. 10 (2021), s. 15781-15793Number of pages 13 s. Language eng - English Country US - United States Keywords Ligands ; Crystal structure ; Metal clusters ; Nanoclusters ; Silver Subject RIV CA - Inorganic Chemistry OECD category Inorganic and nuclear chemistry R&D Projects LTAIN19152 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Method of publishing Limited access Institutional support UACH-T - RVO:61388980 UT WOS 000711790600026 EID SCOPUS 85117202961 DOI 10.1021/acsnano.1c02602 Annotation Noble metal nanoclusters protected with carboranes, a 12-vertex, nearly icosahedral boron-carbon framework system, have received immense attention due to their different physicochemical properties. We have synthesized ortho-carborane-1,2-dithiol (CBDT) and triphenylphosphine (TPP) coprotected [Ag42(CBDT)15(TPP)4]2- (shortly Ag42) using a ligand-exchange induced structural transformation reaction starting from [Ag18H16(TPP)10]2+ (shortly Ag18). The formation of Ag42 was confirmed using UV-vis absorption spectroscopy, mass spectrometry, transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and multinuclear magnetic resonance spectroscopy. Multiple UV-vis optical absorption features, which exhibit characteristic patterns, confirmed its molecular nature. Ag42 is the highest nuclearity silver nanocluster protected with carboranes reported so far. Although these clusters are thermally stable up to 200 °C in their solid state, light-irradiation of its solutions in dichloromethane results in its structural conversion to [Ag14(CBDT)6(TPP)6] (shortly Ag14). Single crystal X-ray diffraction of Ag14 exhibits Ag8-Ag6 core-shell structure of this nanocluster. Other spectroscopic and microscopic studies also confirm the formation of Ag14. Time-dependent mass spectrometry revealed that this light-activated intercluster conversion went through two sets of intermediate clusters. The first set of intermediates, [Ag37(CBDT)12(TPP)4]3- and [Ag35(CBDT)8(TPP)4]2- were formed after 8 h of light irradiation, and the second set comprised of [Ag30(CBDT)8(TPP)4]2-, [Ag26(CBDT)11(TPP)4]2-, and [Ag26(CBDT)7(TPP)7]2- were formed after 16 h of irradiation. After 24 h, the conversion to Ag14 was complete. Density functional theory calculations reveal that the kernel-centered excited state molecular orbitals of Ag42 are responsible for light-activated transformation. Interestingly, Ag42 showed near-infrared emission at 980 nm (1.26 eV) with a lifetime of >1.5 μs, indicating phosphorescence, while Ag14 shows red luminescence at 626 nm (1.98 eV) with a lifetime of 550 ps, indicating fluorescence. Femtosecond and nanosecond transient absorption showed the transitions between their electronic energy levels and associated carrier dynamics. Formation of the stable excited states of Ag42 is shown to be responsible for the core transformation. Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2022 Electronic address https://pubs.acs.org/doi/10.1021/acsnano.1c02602
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