Issue 38, 2024

Ultralow thermal conductivity and thermally-deactivated electrical transport in a 1D silver array with alternating δ-bonds

Abstract

We report the synthesis of a (TMA)AgBr2 (TMA = tetramethylammonium) crystal, which comprises inorganic anionic chains of –(AgBr2)– stabilized by columnar stacks of organic TMA cations with a periodic arrangement of shorter and longer Ag(I)⋯Ag(I) bonds, even though all the Ag(I) ions are chemically equivalent. The presence of two chemically non-equivalent bridging Br ions is attributed to the primary cause of such an unusual arrangement, as clearly visualized in the charge density plot of (TMA)AgBr2 extracted from the theoretical calculations based on density functional theory. Remarkably, we identified from the orbital-projected density of states the existence of alternate δ-like bonding involving dxy orbitals of 4d10 Ag(I), which was attributed to the cause for ultralow thermal conductivity and thermally-deactivated electrical transport in (TMA)AgBr2. Barring the energetics, our observations on the existence of a δ-bond will shed new light in understanding the nature of metal–metal chemical bonding and its unprecedented implications.

Graphical abstract: Ultralow thermal conductivity and thermally-deactivated electrical transport in a 1D silver array with alternating δ-bonds

Supplementary files

Article information

Article type
Edge Article
Submitted
24 Jun 2024
Accepted
28 Aug 2024
First published
29 Aug 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 15907-15912

Ultralow thermal conductivity and thermally-deactivated electrical transport in a 1D silver array with alternating δ-bonds

N. Hassan, S. Nagaraja, S. Saha, K. Tarafder and N. Ballav, Chem. Sci., 2024, 15, 15907 DOI: 10.1039/D4SC04165H

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