Browsing by Author "Sun, Di"

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    Dicarboxylic Acids Induced Tandem Transformation of Silver Nanocluster
    (AMER CHEMICAL SOC, 2023) Wang, Zhi; Gupta, Rakesh Kumar; Alkan, Fahri; Han, Bao-Liang; Feng, Lei; Huang, Xian-Qiang; Gao, Zhi-Yong; Tung, Chen-Ho; Sun, Di; 0000-0002-4046-9044; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Alkan, Fahri
    Structural transformation of metal nanoclusters (NCs) is of great ongoing interest regarding their synthesis, stability, and reactivity. Although sporadic examples of cluster transformations have been reported, neither the underlying transformation mechanism nor the intermediates are unambiguous. Herein, we have synthesized a flexible 54-nuclei silver cluster (Ag54) by combining soft (t BuC�C−) and hard (n PrCOO−) ligands. The existence of weakly coordinated n PrCOO− enhances the reactivity of Ag54, thus facilitating the dicarboxylic acid to induce structural transformation. X-ray structural analyses reveal that Ag54 transforms to Ag28 cluster-based 2D networks (Ag28a and Ag28b) induced by H2suc (succinic acid) and H2glu (glutaric acid), whereas with H2pda (2,2′-(1,2-phenylene)diacetic acid), a discrete Ag28 cluster (Ag28c) is isolated. The key intermediate Ag17 that emerges during the self-dissociation of Ag54 was isolated by using cryogenic recrystallization and characterized by X-ray crystallography. The “tandem transformation” mechanism for the structure evolution from Ag54 to Ag28a is established by time-dependent electrospray ionization mass spectrometry (ESIMS) and UV−vis spectroscopy. In addition, the catalytic activity in the 4-nitrophenol reduction follows the sequence Ag28c > Ag28b > Ag28a > Ag54 due to more bare silver sites on the surface of the Ag28 cluster unit. Our findings not only open new avenues to the synthesis of silver NCs but also shed light on a better understanding of the structural transformation mechanism from one cluster to another or cluster-based metal−organic networks induced by dicarboxylates.
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    An Ultrastable 155-Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion
    (WILEY-V C H VERLAG GMBH, 2022) Wang, Zhi; Alkan, Fahri; Aikens, Christine M.; Kurmoo, Mohamedally; Zhang, Zhen-Yi; Song, Ke-Peng; Tung, Chen-Ho; Sun, Di; 0000-0002-4046-9044; AGÜ, Mühendislik Fakültesi, Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü; Alkan, Fahri
    Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed-valence silver nanocluster [Ag-155(CyS)(40)(TC4A)(5)Cl-2] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p-tert-butylthiacalix[4]arene (H(4)TC4A). Its single-crystal structure consists of a metallic core of four concentric shells, Ag-13@Ag-42@Ag-30@Ag-70, lined with a organic skin of 40CyS(-) and 5TC4A(4-) and 2Cl(-). Ag155 manifests an unusual pseudo-5-fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.