Dianionic bis(benzenesulfonate)–naphthalenediimide (BSNDI^2–) formed simple 2:1 cation–anion salts of (NH₄⁺)₂(BSNDI^2–) (1), (CH₃NH₃⁺)₂(BSNDI^2–) (2), (C₂H₅NH₃⁺)₂(BSNDI^2–) (3), [(C₂H₅)₂NH₂⁺]₂(BSNDI^2–) (4), and [(C₂H₅)₃NH⁺]₂(BSNDI^2–) (5). The thermal stability, crystal structure, electron transport properties, and dielectric response were evaluated for these systems in terms of π-electron density and dimensional crossover from two-dimensional (2D) and one-dimensional (1D) to zero-dimensional (0D) electronic structures. Systematic modification of the counter cations from NH₄⁺ to simple alkylammoniums (CH₃NH₃⁺, C₂H₅NH₃⁺, (C₂H₅)₂NH₂⁺, and (C₂H₅)₃NH⁺) for BSNDI^2– salts affected the packing π-density and dimensionality of NDI π-cores. All single crystals formed alternating cation–anion layers, where the intermolecular interactions in salts 1, 2, 3, 4, and 5 were observed as dense 2D brickstone, 1D column, 1D column, dilute 2D herringbone, and isolated 0D monomer arrangements, respectively. The π-electron occupation percentage in the unit cell of salts 1, 2, 3, 4, and 5 decreased in that order, at 96.2%, 87.8%, 83.8%, 78.8%, and 72.6%, respectively, where the intermolecular π–π interaction between BSINDI^2– anions was gradually diluted on increasing in the cation volume. The transfer integrals between the lowest unoccupied molecular orbital in salts 1–5 clearly indicated a dimensional crossover from 2D to 1D to 0D electronic structures. Flash-photolysis time-resolved microwave conductivity measurements of salts 1, 2, 3, and 4 helped determine the magnitude of electron carrier mobility, which followed the order 1 > 2 ≈ 3 ≈ 4. The dielectric response of salt 1 being an order of magnitude higher than those of salts 2–5 was associated with the protonic conductivity in the NH₄⁺···^–SO₃– electrostatic hydrogen-bonding network layer. Simple cation exchange in dianionic BSNDI^2– salts conventionally modified the intermolecular π–π interactions in terms of dimensionality, magnitude, and electron transport properties.

中文翻译：

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静电结合萘二甲酰亚胺盐中π电子的密度和尺寸控制

双阴离子双（苯磺酸盐）-萘二酰亚胺（BSNDI ^2–）形成（NH ₄ ⁺）₂（BSNDI ^2–）（1），（CH ₃ NH ₃ ⁺）₂（BSNDI ^2–）的简单2：1阳离子-阴离子盐。（2），（C ₂ H ₅ NH ₃ ⁺）₂（BSNDI ^2–）（3），[（C ₂ H ₅）₂ NH ₂ ⁺ ] ₂（BSNDI ^2–）（4）和[（C ₂ H ₅）₃ NH ⁺ ] ₂（BSNDI ^2–）（5）。根据π电子密度和从二维（2D）和一维（1D）到零维（0D）的尺寸交叉，评估了这些系统的热稳定性，晶体结构，电子传输特性和介电响应。电子结构。从NH ₄ ⁺到单烷基铵（CH ₃ NH ₃ ⁺，C ₂ H ₅ NH ₃⁺，（C ₂ H ^ ₅）₂ NH ₂ ⁺，和（C ₂ H ^ ₅）₃ NH ⁺），用于BSNDI ^2-盐影响的填充π密度和维度NDI π型芯体。所有单晶形成交替的阳离子-阴离子层，其中在盐的分子间相互作用1，2，3，4，和5观察到分别为致密的2D砖石，1D柱，1D柱，稀2D人字形和孤立的0D单体排列。以盐的单位单元的π电子占有百分比1，2，3，4，和5的顺序下降，分别为96.2％，87.8％，83.8％，78.8％，和72.6％，其中，分子间π随着阳离子体积的增加，BSINDI ^2–阴离子之间的–π相互作用逐渐被稀释。在盐中最低未占据分子轨道之间的转移积分1 - 5清楚地表明了从2D到1D到0D电子结构的尺寸交叉。闪光光解时间分辨的盐的微波电导率测量1，2，3，和4帮助确定电子载流子迁移的大小，其大小顺序为1 > 2 ≈ 3 ≈ 4。盐1的介电响应比盐2 – 5的介电响应高一个数量级，这与NH ₄ ⁺ ·· ^{– –} SO _3中的质子传导率有关。–静电氢键网络层。传统上，双阴离子BSNDI ^2–盐中的简单阳离子交换在尺寸，大小和电子传输性质方面改变了分子间π–π相互作用。