Interfacing organic molecular groups with well-defined inorganic lattices, especially in low dimensions, enables synthetic routes for the rational manipulation of both their local or extended lattice structures and physical properties. While appreciably studied in two-dimensional systems, the influence of surface organic substituents on many known and emergent one-dimensional (1D) and quasi-1D (q-1D) crystals has remained underexplored. Herein, we demonstrate the surface functionalization of bulk and nanoscale Chevrel-like q-1D ionic crystals using In₂Mo₆Te₆, a predicted q-1D Dirac semimetal, as the model phase. Using a series of alkyl ammonium (−NR₄⁺; R = H, methyl, ethyl, butyl, and octyl) substituents with varying chain lengths, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction with longer chain substituents. Additionally, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction as the alkyl chain substituents become longer using a combination of powder X-ray diffraction and Raman experiments. Beyond the structural modulation that the substituted groups can impose on the lattice, we also found that the substitution of ammonium-based groups on the surface of the nanocrystals resulted in selective suspension in aqueous (NH₄⁺-functionalized) or organic solvents (NOc₄⁺-functionalized), imparted fluorescent character (Rhodamine B-functionalized), and modulated the electrical conductivity of the nanocrystal ensemble. Altogether, our results underscore the potential of organic–inorganic interfacing strategies to tune the structural and physical properties of rediscovered Chevrel-type q-1D ionic solids and open opportunities for the development of surface-addressable building blocks for hybrid electronic and optoelectronic devices at the nanoscale.

中文翻译：

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导电准一维Chevrel型碲化物纳米晶体的功能化和结构演化

将有机分子基团与明确的无机晶格连接，特别是在低维度下，可以实现合理操纵其局部或扩展晶格结构和物理性质的合成路线。虽然在二维系统中进行了相当多的研究，但表面有机取代基对许多已知和新兴的一维 (1D) 和准 1D (q-1D) 晶体的影响仍未得到充分研究。在此，我们使用 In ₂ Mo ₆ Te ₆（一种预测的 q-1D 狄拉克半金属）作为模型相，演示了块状和纳米级 Chevrel 状 q-1D 离子晶体的表面功能化。使用一系列具有不同链长的烷基铵（−NR ₄ ⁺；R = H、甲基、乙基、丁基和辛基）取代基，我们证明了链内c轴方向的系统扩张和链间a的收缩/b-轴方向具有较长链取代基。此外，我们结合粉末 X 射线衍射和拉曼实验证明了随着烷基链取代基变长，链内c轴方向的系统扩展和链间a/b轴方向的收缩。除了取代基团可以对晶格施加的结构调节之外，我们还发现纳米晶体表面上的铵基基团的取代导致选择性悬浮在水性（NH ₄ ⁺官能化）或有机溶剂（NOc ₄ ⁺ -功能化），赋予荧光特性（罗丹明 B-功能化），并调节纳米晶体整体的电导率。总而言之，我们的结果强调了有机-无机界面策略在调整重新发现的 Chevrel 型 q-1D 离子固体的结构和物理性质方面的潜力，并为混合电子和光电器件的表面可寻址构建块的开发提供了机会。纳米级。