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

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Ultralow thermal conductivity and thermally-deactivated electrical transport in a 1D silver array with alternating δ-bonds
Chemical Science ( IF 7.6 ) Pub Date : 2024-08-29 , DOI: 10.1039/d4sc04165h
Nahid Hassan ₁ , Suneetha Nagaraja ₂ , Sauvik Saha ₁ , Kartick Tarafder ₂ , Nirmalya Ballav ₁

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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 d_xy 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.

中文翻译：

具有交替 δ 键的一维银阵列中的超低导热率和热失活电传输

我们报道了 (TMA)AgBr ₂ （TMA = 四甲基铵）晶体的合成，该晶体包含 –(AgBr ₂ ) _∝ – 的无机阴离子链，由有机 TMA 阳离子柱状堆叠稳定，并具有较短和较长 Ag() 的周期性排列⋯Ag() 键，即使所有 Ag() 离子在化学上都是等价的。两个化学上不等价的桥接 Br 离子的存在是造成这种不寻常排列的主要原因，如从基于密度泛函理论的理论计算中提取的 (TMA)AgBr ₂电荷密度图清楚地可见。值得注意的是，我们从轨道投影态密度中识别出涉及 4d ¹⁰ Ag() 的 d _xy轨道的交替 δ 类键合的存在，这归因于 (TMA) 中超低导热率和热失活电传输的原因) 溴化银₂ .除了能量学之外，我们对δ键存在的观察将为理解金属-金属化学键的本质及其前所未有的影响提供新的线索。

更新日期：2024-08-29

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