TY - JOUR
T1 - Polymorphism of [Cu15(PhCH2CH2S)13(PPh3)6][BF4]2 and Double-Helical Assembly of [Cu18H(PhCH2CH2S)14(PPh3)6Cl3]
T2 - Origin of Two Chiral Nanoclusters with Triple-Helical Core from Intermediates
AU - Nag, Abhijit
AU - Butt, Abdul Mannan
AU - Yang, Moon Young
AU - Managutti, Praveen B.
AU - Pirzada, Bilal Masood
AU - Mohideen, M. Infas H.
AU - Abdelhady, Ahmed L.
AU - Haija, Mohamed Abu
AU - Mohamed, Sharmarke
AU - Merinov, Boris V.
AU - Goddard, William A.
AU - Qurashi, Ahsanulhaq
N1 - Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.
PY - 2025/2/3
Y1 - 2025/2/3
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/85217235940
U2 - 10.1021/acsmaterialslett.4c02148
DO - 10.1021/acsmaterialslett.4c02148
M3 - Article
AN - SCOPUS:85217235940
SN - 2639-4979
VL - 7
SP - 442
EP - 449
JO - ACS Materials Letters
JF - ACS Materials Letters
IS - 2
ER -