Hassan, N.Nagaraja, S.Saha, S.Tarafder, K.Ballav, N.2026-02-042024Chemical Science, 2024, 15, 38, pp. 15907-1591220416520https://doi.org/10.1039/d4sc04165hhttps://idr.nitk.ac.in/handle/123456789/20971We report the synthesis of a (TMA)AgBr<inf>2</inf> (TMA = tetramethylammonium) crystal, which comprises inorganic anionic chains of -(AgBr<inf>2</inf>)<inf>∝</inf>- 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)AgBr<inf>2</inf> 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 d<inf>xy</inf> orbitals of 4d10 Ag(i), which was attributed to the cause for ultralow thermal conductivity and thermally-deactivated electrical transport in (TMA)AgBr<inf>2</inf>. 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. © 2024 The Royal Society of Chemistry.Silver halidesSpectroscopic analysisSynthesis (chemical)Anionic chainsColumnar stacksDensity plotsElectrical transportInorganicsOrbitalsOrganicsSilver arraysTetramethylammoniumThermalBromine compounds