Struktur und Eigenschaften des Methylpentafluorphosphatanions, [CH3PF5]—

Structure and Properties of the Methyltetrafluorophosphate Anion, [CH₃PF₅]^— Methyltetrafluorphosphorane reacts with the fluorides NaF, KF, CsF, and (CH₃)₄NF with formation of the corresponding methylpentafluorophosphates. In case of the K and Cs salts K[CH₃PF₅] · CH₃CN and Cs[CH₃PF₅] · CH₃CN, respectively, are formed using acetonitrile as solvent. The salts are characterized by NMR, IR and Raman spectroscopy. The vibrational frequencies are compared with ab initio calculated data (RHF/6‐31+G*). The RHF/6‐31+G* calculation yields for the almost octahedral anion bond distances of d(PF_eq) = 163.7 pm, d(PF_ax) = 162.0 pm, and d(PC) = 184.8 pm.     

Synthese und Eigenschaften von Pentafluorophosphaten,YPF5− (Y = OR,NHAr), und PF5 · Amin-Addukten,PF5 · HNR2

Synthesis and Properties of Pentafluorophosphates, YPF₅^? (Y = OR, NHAr), and PF₅-Amine Adducts, PF₅ · NHR₂ In the presence of secondary amines instead of hexafluorophosphates, PF₆^?, PF₅-amine adducts, PF₅ · NHR₂, are obtained by the reaction of PCl₅ with alkylammonium fluorides in acetonitrile. The additional presence of alcohols or phenol leads to the formation of alkoxy- or aroxypentafluorophosphates, ROPF₅^?. The PF₅-amine adducts can be converted into ROPF₅^? or arylimidopentafluorophosphates, ArNHPF₅^?, resp., by treating with alcohols or aryl amines, resp.     

Linear Pyrazole‐bridged Tetra(N‐heterocyclic carbene) Ligands and Their Hexanuclear Silver(I) Complexes

New hybrid ligands are reported that combine two types of popular donor groups within a single linear scaffold, viz., a central pyrazolate bridge and two appended bis(N‐heterocyclic carbene) units; the ligand strands thus provide two potentially tridentate {NCC} compartments. The pyrazole/tetraimidazolium proligands, [H₅L¹](PF₆)₄ and [H₅L²](PF₆)₄ , were synthesized via multi‐step protocols, and the NH prototropy of [H₅L¹](PF₆)₄ was examined by variable temperature (VT) NMR spectroscopy, giving solvent dependent activation parameters (ΔH^? = 27.6 kJ · mol^–1, ΔS^? = –125 J · mol^–1 · K^–1 in [D₃]MeCN; ΔH^? = 40.4 kJ · mol^–1, ΔS^? = –86.9 J · mol^–1 · K^–1 in [D₆]DMSO) that are in the range typical for pyrazoles. Reaction of the proligands with Ag₂O gave hexametallic complexes [Ag₆(L¹)₂](PF₆)₄ and [Ag₆(L²)₂](PF₆)₄ that involve all six potential donor atoms of the ligands, viz. the four C^NHC and two N^pz donors, in metal coordination. X‐ray crystallography revealed a chair‐like central {Ag₆} deck in both complexes but different arrangements of the ligand strands, which goes along with significantly different Ag^I ··· Ag^I distances that indicate more pronounced argentophilic interactions in case of [Ag₆(L¹)₂]^{4 +}.     

Molecular Recognition Properties of Biphen[4]arene

Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts ( 1? PF₆ and 2? PF₆), pyridinium‐based guests ( 3? 2 PF₆– 6? 2 PF₆), and cobaltocenium hexafluorophosphate ( 7? PF₆), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7‐dibutyldiazapyrenium bis(hexafluorophosphate) ( 4? 2 PF₆) axle to form a [2]pseudorotaxane‐type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2? PF₆ and cobaltocenium 7? PF₆, which have tridimensional shape and relatively large size. The association constant of the 7 ⁺?OHBP4 complex in 1:1 (v/v) [D₆]acetone/CD₂Cl₂ solution is up to 3100±300 m ^?1.     

Reaction of PF5·CH3CN with sulfide

Nitriles react with PF₅ and also with AsF₅, SbF₅ forming 1:1-adducts. Using C₂Cl₃F₃ as a solvent is of advantage for this reaction. PF₅·CH₃CN and [N(C₂H₅)₄]SH give [N(C₂H₅)₄][P₂S₂F₈] with a sulfur double bridge and hexafluorophosphate in acetonitrile [1]. In case of AsF₅·CH₃CN a salt with the anion [AsF₅NHCSCH₃]^? has been isolated [2]. Following products have been confirmed in a reaction mixture of PF₅·CH₃CN and SH^? in acetonitrile by NMR (³¹P and ¹⁹F): [PF₆]^?, [F₅PSPF₅]^2?,

, F₄PSH, F₃PS, HPS₂F₂, [PS₂F₂]^?, [F₅PNC(SH)CH₃]^?, [F₅PNHCSCH₃]^?, [F₅PSH]^?. With a ratio PF₅·CH₃CN: SH^? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products.     

The Structural Systematics of Protonation of Some Important Nitrogen‐base Ligands. IV. Some Ethane‐1,2‐diaminium Univalent Anion Salt/1,10‐Phenanthroline (Hydrate) Arrays

Syntheses and single crystal X‐ray structure characterisations are recorded for some novel series of crystalline complexes formed between salts of univalent anions of the ethane‐1,2‐diaminium cation, [enH₂]X₂, and 1,10‐phenanthroline (‘phen’), variously hydrated, thus: [enH₂]X₂·mphen(·nH₂O), for m = 2, 4 and 10 (one example), n various. In all cases, the motifs constituting the arrays comprise columns of [enH₂]²⁺ cations, carrying the protonic array but linked in a second dimension by hydrogen‐bonding to associated anions and water molecules (where present), expanding the column in some cases to form a sheet, different degrees of hydration compensating for changing anion bulk. In a third dimension the protonic hydrogen complement also links to the nitrogenous component of phen stacks which surround the column. Thus, for the m = 2 array, in a triclinic cell, a, b, c broadly 10‐11 (x2), 7Å, α, β, γ 80, 70° (x2), the cation and phen columns lie parallel to c; in the unsolvated trichloroacetate compound, the cation column is associated with anions to either side, these linking into a sheet with water molecules in the more highly hydrated trifluoroacetate (‘tfa’) and nitrate (n = 2), and chloride and bromide (n = 4) arrays (the tfa adduct a superlattice doubled in c). In the m = 4 arrays, an additional phen stack is inserted, forming a sheet with the first in the second dimension for the perchlorate tetrahydrate array, the iodide pentahydrate counterpart being a 2 x c superlattice. A second nitrate salt, m = 10, n = 4, is also described, a complex array of multiple networks of the above type. Single crystal X‐ray structure determinations are also recorded for salts [phenH](PF₆)·phen and [2,9‐Me₂phenH](PF₆). In the phen adduct, the protonic hydrogen atom is closely associated (N···H 0.90(4) Å) with one of the two independent phen moieties, these disposed alternately in a stack up b close to the 2₁ screw axis, so that the hydrogen bridges to the unprotonated moiety (H···N′ 2.36(4) Å) pitched at an angle of 47° to it in the screw‐related stack. In the Me₂phen salt, the phen moieties lie in crystallographic mirror planes, normal to and stacked up b, with the protonic hydrogen atom contacting a PF₆ fluorine atom (H···F 1.96(3) Å). The structure of unsolvated Me₂phen is also recorded.     

对氨基苯甲酸热力学性质的量热和热分析研究

在80～400 K温区,用高精度全自动绝热量热仪测定了对氨基苯甲酸摩尔热容,得到摩尔热容随温度的变化的关系式为：     

Impact of the anion and chalcogen on the crystal structure and properties of 4,6‐dimethyl‐2‐pyrimido(thio)nium halides

By the reaction of urea or thiourea, acetylacetone and hydrogen halide (HF, HBr or HI), we have obtained seven new 4,6‐dimethyl‐2‐pyrimido(thio)nium salts, which were characterized by single‐crystal X‐ray diffraction, namely, 4,6‐dimethyl‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium bifluoride, C₆H₉N₂O⁺·HF₂^? or (dmpH)F₂H, 4,6‐dimethyl‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium bromide, C₆H₉N₂O⁺·Br^? or (dmpH)Br, 4,6‐dimethyl‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium iodide, C₆H₉N₂O⁺·I^? or (dmpH)I, 4,6‐dimethyl‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium iodide–urea (1/1), C₆H₉N₂O⁺·I^?·CH₄N₂O or (dmpH)I·ur, 4,6‐dimethyl‐2‐sulfanylidene‐2,3‐dihydropyrimidin‐1‐ium bifluoride–thiourea (1/1), C₆H₉N₂S⁺·HF₂^?·CH₄N₂S or (dmptH)F₂H·tu, 4,6‐dimethyl‐2‐sulfanylidene‐2,3‐dihydropyrimidin‐1‐ium bromide, C₆H₉N₂S⁺·Br^? or (dmptH)Br, and 4,6‐dimethyl‐2‐sulfanylidene‐2,3‐dihydropyrimidin‐1‐ium iodide, C₆H₉N₂S⁺·I^? or (dmptH)I. Three HCl derivatives were described previously in the literature, namely, 4,6‐dimethyl‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium chloride, (dmpH)Cl, 4,6‐dimethyl‐2‐sulfanylidene‐2,3‐dihydropyrimidin‐1‐ium chloride monohydrate, (dmptH)Cl·H₂O, and 4,6‐dimethyl‐2‐sulfanylidene‐2,3‐dihydropyrimidin‐1‐ium chloride–thiourea (1/1), (dmptH)Cl·tu. Structural analysis shows that in 9 out of 10 of these compounds, the ions form one‐dimensional chains or ribbons stabilized by hydrogen bonds. Only in one compound are parallel planes present. In all the structures, there are charge‐assisted N⁺—H…X^? hydrogen bonds, as well as weaker C_Ar⁺—H…X^? and π⁺…X^? interactions. The structures can be divided into five types according to their hydrogen‐bond patterns. All the compounds undergo thermal decomposition at relatively high temperatures (150–300 °C) without melting. Four oxopyrimidinium salts containing a π⁺…X^?…π⁺ sandwich‐like structural motif exhibit luminescent properties.     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

An Internal Fluorescent Probe Based on Anthracene to Evaluate Cation–Anion Interactions in Imidazolium Salts

A series of fluorescent imidazolium‐based salts containing the cation [AnCH₂MeIm]⁺ (in which An=anthracene and Im=the imidazolium cation) with Cl^?, BF₄^?, PF₆^?, SO₃CF₃^?, [N(CN)₂]^?, [N(SO₂CF₃)₂]^?, or PhBF₃^? anions have been prepared and characterized. X‐ray diffraction analysis of four of the salts reveals a number of C? H???X‐type (X=O, N, F) hydrogen bonds between the hydrogen atoms from the imidazolium ring and in some cases from the anthracene ring with the electronegative atoms of the anions. Additionally, C? H???π interactions can be found in all the salts analyzed by X‐ray diffraction, whereas π–π stacking is observed only in the salt containing the phenyltrifluoroborate anion. Fluorescence emission analysis in acetonitrile shows that the fluorescence of these salts varies significantly according to the nature of the anion, and correlates to the extent of ion pairing present in solution. Photodimerization of these salts was observed, and in one case a dimer has been isolated and characterized by X‐ray crystallography.     

2-甲基-2-丁醇的低温热容和热力学性质

本文用精密自动绝热量热仪测定了2-甲基-2-丁醇在80～305 K温区的热容,从热容曲线(Cp-T) 发现三个固－固相变和一个固－液相变, 其相变温度分别为T = 146.355, 149.929, 214.395, 262.706 K。从实验热容数据用最小二乘法得到以下四个温区的热容拟合方程。在80～140K温区, Cp,m = 39.208 + 8.0724X - 1.9583X2 + 10.06X3 + 1.799X4 - 7.2778X5 + 1.4919X6, 折合温度X = (T –110) / 30; 在 155 ～ 210 K温区, Cp,m = 70.701 + 10.631X + 12.767X2 + 0.3583X3 - 22.272X4 - 0.417X5 + 12.055X6, X = (T –182.5) /27.5; 在220 ～ 250 K温区, Cp,m = 99.176 + 7.7199X - 26.138X2 + 28.949X3 + 0.7599X4 - 25.823X5 + 21.131X6, X = (T – 235)/15; 在 270～305 K温区, Cp,m =121.73 + 16.53 X- 1.0732X2 - 34.937X3 - 19.865X4 + 24.324X5 + 18.544X6, X = (T –287.5)/17.5。从实验热容计算出相变焓分别为0.9392, 1.541, 0.6646, 2.239 kJ×mol-1; 相变熵分别为6.417, 10.28, 3.100, 8.527 J×K-1×mol-1。根据热力学函数关系式计算出80～305 K温区每隔5 K的热力学函数值 [HT –H298.15]和 [ST –S298.15]。     

新的杯[4]芳烃衍生物通过缔合乙腈进行自插入的X-射线衍射和密度泛函理论研究

合成和表征了一个新的杯[4]芳烃衍生物，11,23-二羟亚胺甲基-25,27-二羟基-26,28-二丙氧基杯[4]芳烃 (B)及其与乙腈生成的组成为B·2CH₃CN的化合物。¹H NMR显示，在B·2CH₃CN中B采取锥型构象，X-射线衍射分析确证在溶液中所发现的构象。在晶格网络中存在着B·2CH₃CN以二聚体形式的自插入现象。在B3LYP/6-311G(d)水平上计算了该自插入二聚体中的非共价相互作用能，并对基集叠加误差进行了校正。在二聚体中的B·2CH₃CN，一个CH₃CN通过与羟亚胺基形成氢键使之稳定，结合能为–5.02 kJ·mol^-1，另一个CH₃CN则通过与另一个羟亚胺基形成氢键以及与另一B·2CH₃CN中B苯环空腔间的C–H···π相互作用使之稳定，结合能分别为–14.23 kJ·mol^-1和–3.77 kJ·mol^-1。自插入的驱动能为–7.54 kJ·mol^-1。     

二维多孔铜-间苯二腈配位聚合物用于阴离子交换及客体分子可逆吸附性的研究

The 2D porous copper（Ⅰ） complex with 1,3-dicyanobenzene （DCB）, [Cu（DCB）2]（PF6）（Me2CO） 1, exhibits channels along axis c, in which one molecule acetone and one anion PF6 per formula unit are included respectively. The reversible incorporation of guest acetone and acetonitrile, as well as the anion exchange from PF6^- to BF4^- or CF3SO3^-, was investigated by thermogravimetric （TG） analysis, ^1H NMR spectra and/or infrared absorption spectroscopy. Additionally, the incorporation of benzene and toluene into complex 1 was also discussed. Complex 1 exhibited size selectivity for guest inclusion or anion exchange.     

Neutral 4‐phenyl‐1‐[phenyl(pyridin‐2‐yl)methylidene]semicarbazide and its salt forms with inorganic anions

Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spectroscopic characterization (IR and NMR spectroscopy) of four such compounds, namely the neutral molecule 4‐phenyl‐1‐[phenyl(pyridin‐2‐yl)methylidene]semicarbazide, C₁₉H₁₆N₄O, (I), abbreviated as HBzPyS, and three different hydrated salts, namely the chloride dihydrate, C₁₉H₁₇N₄O⁺·Cl^?·2H₂O, (II), the nitrate dihydrate, C₁₉H₁₇N₄O⁺·NO₃^?·2H₂O, (III), and the thiocyanate 2.5‐hydrate, C₁₉H₁₇N₄O⁺·SCN^?·2.5H₂O, (IV), of 2‐[phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium, abbreviated as [H₂BzPyS]⁺·X^?·nH₂O, with X = Cl^? and n = 2 for (II), X = NO₃^? and n = 2 for (III), and X = SCN^? and n = 2.5 for (IV), showing the influence of the anionic form in the intermolecular interactions. Water molecules and counter‐ions (chloride or nitrate) are involved in the formation of a two‐dimensional arrangement by the establishment of hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in the solid state. The neutral HBzPyS molecule crystallized as the E isomer due to the existence of weak π–π interactions between pairs of molecules. The calculated IR spectrum of the hydrated [H₂BzPyS]⁺ cation is in good agreement with the experimental results.     

Modulating the Binding of Polycyclic Aromatic Hydrocarbons Inside a Hexacationic Cage by Anion–π Interactions

We report the template‐directed synthesis of BlueCage⁶⁺, a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron‐poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage?6 PF₆ exhibits a lower association constant K_a than its progenitor ExCage?6 PF₆. A close inspection reveals that the six PF₆^? counterions of BlueCage⁶⁺ occupy the cavity in a fleeting manner as a consequence of anion–π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the K_a value for pyrene in BlueCage⁶⁺ when the PF₆^? counterions are replaced by much bulkier anions. The presence of anion–π interactions is supported by X‐ray crystallography, and confirms the presence of a PF₆^? counterion inside its cavity.     

The preparation of copper(II) and copper(I) salts in acetonitrile using group VA and VB pentafluorides

Copper(II) fluorine reacts with the pentafluorides, TaF₅, PF₅, and AsF₅, in acetonitrile to give solvated Cu^II, hexafluoroanion salts. These react with copper metal to give the corresponding Cu^I compounds. Similar reactions occur between AsF₅ and silver(I) or thallium(I) fluorides, but silver(II) fluoride reacts with MeCN, and Ag^I hexafluoroarsenate is formed. PF₅ oxidises Cu slowly in MeCN to give Cu^I hexafluorophosphate, but AsF₅ has no oxidising ability towards metals in MeCN. Spectroscopic data for Cu(MF₆)₂·5MeCN and Cu(MF₆)·4MeCN (M = Ta or P) are discussed.     

Design,synthesis, and self‐assembly manipulating of polymerized ionic liquids contained imidazolium based on “Jacketing” effect

A series of novel polymerized ionic liquids (PILs) contained imidazolium, poly (2,5‐bis{[6‐(1‐butyl‐3′‐imidazolium)hexyl] oxy carbonyl}styrene salts) (denoted as P1? X^?, X^??Br^?, BF₄^?, PF₆^? and TFSI^?) were successfully synthesized via radical polymerization. The chemical structures of the monomers and their corresponding PILs were confirmed by ¹H NMR, ¹³C NMR, and Fourier transform infrared spectroscopy. Thermogravimetric analysis results showed that these PILs had excellent thermal stability. The phase transitions and liquid‐crystalline (LC) behaviors of these polymers were investigated by differential scanning calorimetry, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction. The combined experimental results showed that all the PILs could form hexagonal columnar (?H) LC ordered structures because of the strong interaction between the anions and cations in the side groups except for P1? TFSI^?. The conductivities of monomers and PILs were sketchily investigated, and monomers had higher conductivities than those of conprespoding PILs. For comparison, we have synthesized a polymer without counter‐anion, but similar to the chemical structure of P1? X^?, poly (2, 5‐bis{[6‐(4‐butoxy‐4′‐oxy phenyl) hexyl] oxycarbonyl} styrene) (denoted as P2). In this case, phenyl took place of imidazolium of side chain, and LC ordered structure did not form. The comparison between P1? X^? and P2 suggested that ion played an important role in the constructing of LC ordered structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Oxythiamine hexafluorophosphate monohydrate,a thiamine antagonist with the same conformation as ­thiamine

In the title compound, 3‐[(3,4‐di­hydro‐2‐methyl‐4‐oxopyrimidin‐5‐yl)­methyl]‐5‐(2‐hydroxy­ethyl)‐4‐methyl­thia­zolium hexa­fluoro­phosphate monohydrate, C₁₂H₁₆N₃O₂S⁺·PF₆^?·H₂O, oxy­thi­amine is a monovalent cation with a neutral oxo­pyrimidine ring. The mol­ecule assumes the F conformation, which is a common form for thi­amine but which is substantially different from the unusual V conformation found in the chloride and hydro­chloride salts of oxy­thi­amine. The anion‐bridging interaction, C—H?anion?pyrimidine, is emphasized as being important for stabilization of the F conformation.     

Anion‐Dependent Tendency of Di‐Long‐Chain Quaternary Ammonium Salts to Form Ion Quadruples and Higher Aggregates in Benzene

The self‐aggregation tendency of [N(CH₃)₂(C₁₈H₃₇)₂]X [ 1 X; X^?=BF₄^?, PF₆^?, OTf^?, NTf₂^?, BPh₄^?, BTol₄^?, BAr^F?, and B(C₆F₅)₄^?] salts to form ion quadruples (IQs) and higher aggregates (HAggs) in [D₆]benzene is investigated by means of diffusion NMR spectroscopy. The experimental results indicate that salts containing small anions ( 1 BF₄, 1 PF₆, and 1 OTf) are present in solution as IQs even at the lowest investigated concentration of C=5×10^?5 M and show a limited tendency to further self‐aggregate, reaching a maximum average aggregation number (N=V_H/${V_{\rm{H}}^{{\rm{0IP}}} }$ , where V_H=measured hydrodynamic volume and ${V_{\rm{H}}^{{\rm{0IP}}} }$ =hydrodynamic volume of the ion pair) of about 6–8 (C=0.050–0.100 M ). Salts with larger counterions [ 1 BPh₄, 1 BTol₄, 1 BAr^F, and 1 B(C₆F₅)₄] form instead ion pairs at low concentration but steadily self‐aggregate (especially the non‐fluorinated ones) on increasing their concentration up to N values exceeding 50 (C=0.030–0.050 M ). 1 NTf₂ behaves in an intermediate fashion. The self‐aggregation tendency of salts is quantified by formulating the dependence of V_H on C by means of the equations of indefinitive aggregation models. The following rankings for the formation of IQs and HAggs are obtained: IQs: 1 BF₄≈ 1 PF₆≈ 1 OTf> 1 NTf₂> 1 B(C₆F₅)₄≥ 1 BPh₄≥ 1 BTol₄≥ 1 BAr^F; HAggs: 1 BTol₄> 1 BPh₄> 1 NTf₂> 1 B(C₆F₅)₄> 1 BAr^F> 1 BF₄≈ 1 PF₆≈ 1 OTf. Interionic NOE NMR studies and DFT calculations were conducted in order to determine the relative anion–cation orientation in the self‐aggregating units.