Polymorphism of [Cu15(PhCH2CH2S)13(PPh3)6][BF4]2 and Double-Helical Assembly of [Cu18H(PhCH2CH2S)14(PPh3)6Cl3]: Origin of Two Chiral Nanoclusters with Triple-Helical Core from Intermediates
Abhijit Nag, Abdul Mannan Butt, Moon Young Yang, Praveen B. Managutti, Bilal Masood Pirzada, M. Infas H. Mohideen, Ahmed L. Abdelhady, Mohamed Abu Haija, Sharmarke Mohamed, Boris V. Merinov, William A. Goddard III* and Ahsanulhaq Qurashi*,
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引用次数: 0
Abstract
Here, we report the solvent-induced polymorphism in [Cu15(PET)13(TPP)6][BF4]2(Cu15) (TPP = triphenylphosphine, PET = 2-phenylethanthiol), and double-helical assembly of the [Cu18H(PET)14(TPP)6Cl3] (Cu18) nanocluster (NC) from reaction intermediates. Both copper NCs have an intrinsically chiral triple-stranded helicate metal core, unlike traditional copper NCs with a polyhedral-based kernel. The chiral structure of Cu15 resembles an enantiomeric pair in the unit cell. Moreover, Cu18 has a three-layered 3D chirality of a sandwich constructed of sulfur-bridged copper NCs aligned in a top-middle-down configuration. Furthermore, the Cu18 NC self-hierarchically assembles into a complex double-stranded helix secondary structure sustained by noncovalent interactions. Electrospray ionization mass spectrometry (ESI-MS), density functional theory (DFT), and X-ray photoelectron spectroscopy (XPS) were utilized to validate the single-crystal X-ray diffraction (SCXRD) data. Overall, this study provides an interesting example of polymorphism, chirality, and hierarchical double-helical assembly of NCs, allowing for extensive understanding of complicated structures at the atomic level.
期刊介绍：
ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.
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