Revealing the nature of size and odd/even effect observed by NanoDSC in 2D organic metal chalcogenides: atomic resolution crystallography via diffraction and ab initio calculations

ORAL

Abstract

Layered silver alkanethiolate (AgSCn) is currently of growing scientific interest as 2D organic metal chalcogenides. Exploring the structure of AgSCn with atomic resolution is critical to understand its size and odd/even effect observed in properties such as melting point/enthalpy (NanoDSC). Crystallography determination is often challenging for beam-sensitive hybrid materials with small crystal sizes. In this work, we innovatively overcome this obstacle by combining synchrotron powder X-ray diffraction, nanobeam electron diffraction, and ab initio calculations. Preliminary findings show AgSCn structure consisting of three segments: (i) Ag-S inorganic backbone, which undergoes deformation modulated by organic chain length due to the lattice mismatch between Ag-S framework and the epitaxial hydrocarbon chains; (ii) Interlayer interface: the structural origin of odd/even effect lies in the parity-dependent H-H interactions exhibited among the terminal methyl groups; (iii) Alkyl chains: the epitaxial mismatch between the backbone and the alkyl chains triggers the progression of distortion in the local alkyl configurations towards the optimal chain packing.

*NSF DMR 1409953
NSF DMR 1809573

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Presenters

  • Jie Zhao

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

Authors

  • Jie Zhao

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Zichao Ye

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Kisung Kang

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign
    • University of Illinois at Urbana-Champaign

  • Yu-Tsun Shao

    • Cornell University
    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Scott McCormack

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Mikhail Efremov

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Andre Schleife

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign
    • University of Illinois at Urbana-Champaign

  • Jian-Min Zuo

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign
    • University of Illinois at Urbana Champaign

  • Waltraud Kriven

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign

  • Leslie Allen

    • Department of Material Science and Engineering and Coordinated Science Laboratory, University of Illinois at Urbana-Champaign