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Hydrogen-bonded structure and mechanical chiral response of a silver nanoparticle superlattice

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Self-assembled nanoparticle superlattices—materials made of inorganic cores capped by organic ligands, of varied structures, and held together by diverse binding motifs—exhibit size-dependent properties as well as tunable collective behaviour arising from couplings between their nanoscale constituents1,2,3,4,5,6,7,8,9,10,11,12,13,14,15. Here, we report the single-crystal X-ray structure of a superlattice made in the high-yield synthesis16 of Na4Ag44(p-MBA)30 nanoparticles, and find with large-scale quantum-mechanical simulations that its atomically precise structure and cohesion derive from hydrogen bonds between bundled4p-MBA ligands. We also find that the superlattice’s mechanical response to hydrostatic compression is characterized by a molecular-solid-like bulk modulus B0 = 16.7 GPa, exhibiting anomalous pressure softening and a compression-induced transition to a soft-solid phase. Such a transition involves ligand flexure, which causes gear-like correlated chiral rotation of the nanoparticles. The interplay of compositional diversity, spatial packing efficiency, hydrogen-bond connectivity, and cooperative response in this system exemplifies the melding of the seemingly contrasting paradigms of emergent behaviour ‘small is different’9 and ‘more is different’17.

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Figure 1: Ag44(p-MBA)30.Na4 superlattice structure.
Figure 2: Superlattice compression, and rotational structural transition.
Figure 3: Intra- and inter-NP distances and angles induced by the applied compression (V/V0) of the superlattice.

Change history

  • 14 April 2014

    In the version of this Letter originally published online, in Fig. 1a, the yellow arrow was duplicated. This error has now been corrected in all versions of the Letter.


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The work at GATECH by B.Y., R.N.B., W.D.L. and U.L. was supported by a grant from the Air Force Office of Scientific Research, and the work of J.G. was supported by the Office of Basic Energy Sciences of the US Department of Energy under Contract No. FG05-86ER45234. Computations were made at the Georgia Tech Center for Computational Materials Science. Work at the University of Toledo was supported by NSF grants CHE-1012896 and CRIF-0840474.

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U.L. conceived and directed the theoretical work, analysed the experimental and theoretical results, and wrote the manuscript. B.Y. performed the DFT computations. B.Y., W.D.L., R.N.B. and J.G. participated in the analysis of the computational and experimental results. T.P.B. conceived, directed and analysed the experimental research, and A.D. and B.E.C. performed the experimental work. All authors contributed to preparation of the final manuscript.

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Correspondence to Uzi Landman.

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Yoon, B., Luedtke, W., Barnett, R. et al. Hydrogen-bonded structure and mechanical chiral response of a silver nanoparticle superlattice. Nature Mater 13, 807–811 (2014).

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