Study of free volume parameters of polystyrenes of different molecular architecture by positron annihilation lifetime measurement

Differences of size, content and size distribution of free volumes in linear branched and three-armed polystyrenes, synthesized by radical and anionic processes, were observed by positron annihilation lifetime measurements. The temperature dependence of an average free volume radius was quite similar among polystyrenes of different architectures and molecular weight distributions. The free volume radius increased with temperature, from 0.27 nm (T:60 K) to 0.29 nm (T:260 K) and 0.30 nm (T _g:363 K), then to 0.35 nm (423 K), showing turning at and transition temperature. The free volume content decreased from 60 K to 220 K to 300 K showing peculiar minimum at 220 K to 300 K depending on the molecular shape, increased above 320 K, upto 340 to 360 K. The free volume contents decreased with an increase of molecular weight and by an addition of oligomer or plasticiser, suggesting differences in relaxation time or molecular motion between the edge and middle portions of molecular chain and filling effect of smaller molecules in free volumes, respectively. The apparent free volume fraction showed clear variations atT andT _g. Size distribution of free volumes suggested more complicated behavior of free volume upon the molecular relaxations and filling effect.     

Electronic structures and MCD spectra of trigonal Cr(III)S6 systems

MCD, electronic absorption, external heavy atom, and crystal field data are presented for the low energy region (² E _g, ² T _1g, ⁴ T _2g) and high energy region (² T _2g, ⁴ T _1g) of Cr(dtp)₃, Cr(dtc)₃, and Cr(exan)₃. At low energy, MCD intensities of ² E(² E _g) and ² E(² T _g) are as large or larger than ⁴ T _2g, and the MCD technique is advantageous over electronic absorption in this respect. The MCD positions of ² E _g and ² T _1g are nearly the same for these molecules ( 13 kK and 13.6 kK) · ⁴ T _2g of this region appears trigonally split ( 500 cm^–1) in the MCD of dtp but to a smaller extent than in the electronic crystal spectrum of Lebedda and Palmer ( 600 cm^–1). MCD did not resolve such components for exan and dtc. The higher energy region includes ² T _2g and ⁴ T _1g, and the combined MCD and electronic absorption data of the three compounds taken together lead us to conclude the ordering ² A ₁(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). The potentially useful external heavy atom affect on the solution-observed electronic ² E and ⁴ E bands of Cr(dtp)₃ did not shed additional light on this order of E states. Finally, it is concluded that the order of ⁴ T _1g and ² T _2g cannot be decided from O _h crystal field calculations because of experimental uncertainties about choosing centers of gravity. In addition, ⁴ T _1g and ² T _2g are close together so that ordering ² E<⁴ E does not guarantee ² T _2g<⁴ T _1g. However, it can be concluded that the ratio C/B4 is not correct, whereas the larger 7<(C/B)<8 is consistent with the data of all three molecules because of small B parameters ( 0.4). Locating OO transitions may somewhat decrease C/B and Dq.

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Zusammenfassung In der vorliegenden Arbeit werden folgende Meßergebnisse mitgeteilt; MCD, elektronische Absorption, Einfluß eines äußeren schweren Atoms sowie Kristallfelddaten für den Bereich niedriger Energie (² E _g, ² T _1g, ⁴ T _2g) und den Bereich hoher Energie (² T _2g, ⁴ T _1g) von Cr(dtp)₃, Cr(dtc)₃ und Cr(exan). Bei niedriger Energie sind die MCD-Intensitäten von ² E(² E _g) und ² E(² T _1g) genau so groß, oder größer als ⁴ T _2g, und die MCD-Technik bietet Vorteile gegenüber der elektronischen Absorptionsmethode. Die MCD-Werte von ² E _g und ² T _1g sind für die genannten Moleküle etwa gleich ( 13 kK und 13,6 kK). ⁴ T _2g dieses Gebietes erscheint trigonal aufgespalten ( 500 cm^–1) bei MCD von dtp, aber in einem geringeren Maß als im elektronischen Kristallspektrum von Lebedda und Palmer ( 600 cm^–1) MCD löste solche Komponenten bei exan und dtc nicht auf. Der Bereich höherer Energie enthält ² T _2g und ⁴ T _1g, und aus der Kombination von Daten der MCD-Methode sowie der elektronischen Absorption schlossen wir auf die Anordnung ² A _1g(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). Der möglicherweise nützliche Effekt eines äußeren schweren Atoms auf die in Lösung beobachteten elektronischen ² E- und ⁴E-Banden von Cr(dtp)₃ brachte bezüglich dieser Anordnung der E-Zustände nichts Neues. Weiterhin wird gefolgert, daß die Ordnung von ⁴ T _1g und ² T _2g nicht aus O _h-Kristallfeldberechnungen entschieden werden kann, da experimentelle Unsicherheiten bezüglich der Wahl von Schwerpunkten bestehen. Außerdem liegen ⁴ T _1g und ² T _2g nahe zusammen, sodaß aus der Anordnung ² E<⁴ E nicht notwendig ² T _2g<⁴ T _1g folgt. Es kann jedoch gefolgert werden, daß das Verhältnis C/B4 nicht korrekt ist, während 7<(C/B)<8 konsistent mit den Daten aller drei Moleküle ist, da die B-parameter klein sind (0,4). Die Vokalisierung der OO-Übergänge könnten C/B und Dq etwas erniedrigen.

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Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.

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NDEA Pre-Doctoral Fellow.     

Über einige Komplexboride von Übergangsmetallen

Zusammenfassung Dreistofflegierungen in dem Kombinationen {Mo, W}-{Fe, Co, Ni}-B; {V, Nb, Ta, Mo, W}-B-Al werden vornehmlich auf die Existenz von Komplexboriden hin untersucht. Die isotypen Phasen Mo₂CoB₂, Mo₂NiB₂, W₂FeB₂, W₂CoB₂ und W₂NiB₂ sind strukturell mit Mo₂FeB₂ verwandt, aber doch von dieser Phase verschieden. Gefunden werden außerdem die isotypen Phasen MoCoB und WCoB. Das Problem der -Phase wird diskutiert. In manchen Fällen tritt ein Zwischenzustand auf, der vermutlich durch Stapelfehler einer Unterzelle (c/3 in hexagonaler Aufstellung) hervorgerufen wird. Neben dem Auftreten ternärer Phasen bei Nb-B-Al und Ta-B-Al wird eine ausgeprägte Mischphasenbildung: (Nb, Al)B₂ und (Ta, Al)B₂ beobachtet. Der Dreistoff: Mo-B-Al ist durch die ternäre Phase MoBAl gekennzeichmet, ferner tritt der durch Al stabilisierte CrB-Typ auf (Mo_0,45B_0,50Al_0,05). Die Gleichgewichtsverhältnisse in denT-B-Al-Dreistoffen werden abgeschätzt.

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Alloys of the combinations {Mo, W}-{Fe, Co, Ni}-B, {V, Nb, Ta, Mo, W}-B-Al have been examined with respect to the existence of complex borides. The phases of the approximate formula Mo₂CoB₂, Mo₂NiB₂, W₂FeB₂, W₂CoB₂ and W₂NiB₂ have been found to be isotypic. They do however not correspond to Mo₂FeB₂ having U₃Si₂ structure. Two other complex borides of formula MoCoB and WCoB have been detected having the same crystal structure. The problem of the -phases which partially contain boron will be discussed considering the supposedly occurring stacking faults of a subcell unit (c=c/3 for hexagonal symmetry). Besides formation of ternary compounds for: Nb-B-Al and Ta-B-Al an extended solid solution (Nb, Al)B₂ and (Ta, Al)B₂ has been observed. The Mo-B-Al-system is characterized by the ternary phase of formula MoBAl. Mo-monoboride having CrB-type has been found to be stabilized by a small amount of Al, thus Mo_0,45B_0,50Al_0,05 being formed. The phase equilibria within the ternary systems have been established for the major part.

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Mit 4 Abbildungen     

Donorstärken in 1,2-Dichloräthan

Zusammenfassung Kalorimetrische und spektrophotometrische Untersuchungen über die Donorstärke einer Anzahl nicht-wäßriger Lösungsmittel zeigen, daß die relative Reihung der Donorstärken unabhängig von der Natur des Akzeptors ist. Die Donorreihung lautet gegenüber SbCl₅, Jod und Phenol folgendermaßen: Pyridin > Dimethylsulfoxid > Dimethylacetamid Dimethylformamid > > Trimethylphosphat Diphenylphosphoroxychlorid > Diäthyläther > Aceton > Propandiol-1,2-carbonat > Acetonitril > > Selenoxychlorid Phosphoroxychlorid Benzoylchlorid > > Thionylchlorid > Sulfurylchlorid.

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Calorimetric and spectrophotometric work on the donor strength of various non-aqueous solvents have shown that the relative order of donor strength is independent from the nature of the acceptor. The order of donor strength towards SbCl₅, I₂ and phenole is pyridine > dimethylsulfoxide > dimethylacetamide dimethylformamide > trimethylphosphate diphenylphosphonic chloride > diethyl ether > acetone > propane diol-1,2-carbonate > acetonitrile > selenium oxychloride phosphorus oxychloride benzoyl chloride > thionyl chloride > sulfuryl chloride.

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Exact and approximate forms of the kinetic energy functional<Emphasis Type="Italic"> T</Emphasis><Subscript>s</Subscript>[ρ] for molecules obtained via local-scaling transformations

By means of a constructive procedure based on local-scaling transformations, we have obtained the following exact form for the noninteractive kinetic energy functional of general molecular systems: where (r) is the local-scaling transformation function, T _W[] is the von Weiszäcker term and ^l _N (r _l ) and ^l _N (r _l ) are the radial and angular enhancement factors, respectively, within an atomic domain _I. The terms ^C _N (r _l ) and ^C _N (r _l ) (where C stands for complement of I) contain all contributions to the radial and angular enhancement factors within _I coming from the tails of functions centered on nuclei outside _I. Also, in the context of an atoms-in-a-molecule approach, we discuss the construction of approximations to the kinetic energy enhancement factors appearing in the previous expression for T _s[]. Acknowledgement.The authors gratefully acknowledge support of this work by FONACIT of Venezuela through Group Project No. G-97000741.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002)     

1A1⇔5T2 Spin Transition in Heterometallic Solid Phases FexNi1-x(Htrz)3(NO3)2 · H2O (Htrz = 1,2,4‐Triazole)

Solid phases Fe_xNi_1-x(Htrz)₃(NO₃)₂ · H₂O (0.4 x 0.8$) and Ni(Htrz)₃(NO₃)₂ · H₂O were synthesized and studied. The phases were studied by means of magnetochemistry, powder Xray difraction analysis, and electronic and IR spectroscopy. The heterometallic phases are described by the stoichiographic method of differentiating dissolution (DD). The values of x were determined by two methods — atomic absorption and DD. Magnetochemical data showed that the solid phases exhibit a hightemperature ¹A₁ ⁵T₂ 0.5 x 0.8 and disappears at x = 0.4. The spin transition is accompanied by thermochromism (color changed from pink to white at 0.6 x 1 and from pink to light lilac at x = 0.5). A decrease in x leads to a decrease in the temperature of the forward (under heating T_c ) and reverse (under cooling T_c ) transitions, a decrease in hysteresis value ( T_c), and a smearing of the spin transition.     

Concentrations of Active Species in the Flowing Afterglow of a Nitrogen Microwave Plasma

Measurements of nitrogen atom density, by means of NO chemical titration, along with an evaluation of the densities of some excited species N ₂ (B, v=11), N ₂ (B, v=2), N ₂ (C, v=0), and N ₂ ⁺ (B,v=0), by means of a spectroscopic study of some bands of dinitrogen, are achieved along the flowing afterglow of a dinitrogen microwave plasma (2450 MHz) for several pressures. The concentrations obtained are in the following range: [N]10 ⁺¹⁵ , [N ₂ (B, 2)]10 ⁺⁹ –10 ⁺¹⁰ , [N ₂ (B, 11)]10 ⁺⁸ –10 ⁺⁹ , [N ₂ (C, 0)]10 ⁺⁶ –10 ⁺⁷ , [N ₂ ⁺ (B,0)]10 ⁺⁶ -10 ⁺⁸ (cm^-3). From a kinetic study of the formation and decay of excited and charged species, an estimation of N ₂ (A, v), N ₂ (X, v, and N ₂ ⁺ (X) densities can be derived: [N ₂ (A, v)]10 ⁺¹² , [N ₂ (X, v6)]10 ⁺¹⁵ –10 ⁺¹⁶ , [N ₂ (X, v12)]10 ⁺¹⁴ –10 ⁺¹⁵ , [N ₂ ⁺ (X)]10 ⁺¹⁰ (cm ^-3 ).     

The synthesis and structure of the [2.2]paracyclophane cluster Ru6C(CO)13(μ 3-η 2:η 2:η 2-C16H16)(PPh3) and a study of the 1H-n.m.r. spectra of [2.2]paracyclophane and benzene clusters

Summary The [2.2]paracyclophane cluster, Ru₆C(CO)₁₄( ₃- ^{2 2 2}-C₁₆H₁₆) (1), undergoes reaction with Me₃NO and triphenylphosphine to yield Ru₆C(CO)₁₃( ₃- ^{2 2 2}-C₁₆H₁₆)(PPh₃) (2), which may also be produced from (1) by thermolysis with PPh₃ in THF. Compound (2) has been fully characterized in solution by spectroscopy and in the solid state by a single crystal X-ray diffraction analysis at 277 K, and its structure is compared with that of the parent cluster, (1). Using the same synthetic procedures, the tricyclohexylphosphine analogue, Ru₆C(CO)₁₃( ₃- ^{2 2 2}-C₁₆H₁₆)(PCy₃) (3), has also been prepared and characterized spectroscopically. A comparison of the chemical shifts of the 577-01 protons in the ¹H-n.m.r. spectra of compounds (1)–(3) together with a variety of other [2.2]paracyclophane and benzene clusters has been made.     

Strategies to vectorize conventional SCF-Cl algorithms

Recent high-performance computers, especially supercomputers, achieve very high-speed operations but bring about serious I/O problems in quantum chemical computations. Strategies to vectorize conventional SCF-CI algorithms are discussed relating to the I/O problems. The conventional SCF-CI algorithm which is proposed here reduces I/O processing by eliminating all sorting routines and redundant integral files and generates directly nonzero and nonredundant PK integrals with a vectorizable canonically-ordered list. The new implementation has been undertaken and successfully realized as a program system named GSCF3. The vector to scalar acceleration rate of GSCF3 on the HITAC S-810 are as follows: 2.5 5 in the AO integral evaluation, 5 12 in the SCF calculation, 15 30 in the four-index integral transformation, 10 20 in the CI matrix diagonalization, and overall 510 through SCF-CI.     

Triplet states of humic acids studied by laser flash photolysis using different excitation wavelengths

The spectra and kinetics of short-lived intermediates formed from aqueous (0.1 N NaOH) solutions of the natural mixture of humic and fulvic acids (HFA) were studied by laser flash photolysis using excitation wavelengths of 337, 390, 470, and 520 nm. Laser photolysis of HFA with light of 520 and 470 nm results in the formation of triplet excited states (T_HFA) characterized by the broad absorption spectrum with a maximum near 630 nm and lifetimes of 0.15 ms in deoxygenated solutions. The formation of two types of T_HFA with lifetimes of 0.1 and 2 ms and absorption spectra with maxima at 570 nm is observed under photolysis with light of 337 and 390 nm. The estimation of quantum yields of T_HFA gives 1 and 0.3% under photolysis with excitation wavelengths of 337 and 520 nm, respectively. The rate constants of T_HFA quenching by molecular oxygen are equal to (7—8)·10⁸ L mol^–1 s^–1.     

Ab initio studies of the low-lying π-states of borazine

Self-consistent-field and configuration-interaction studies were performed on borazine, using a double-zeta basis set augmented by six diffuse -functions. Low-lying singlet and triplet states of the A ₁ , A ₂ and E species were calculated, corresponding to ^* excited valence and Rydberg states. A selection out of singly and doubly excited configurations relative to a set of reference configurations was made for each species. Calculated vertical excitation energies (in eV) are 7.12 for ¹ A ₂(V), 8.45 for ¹ E (3p-R), 8.57 for ¹ A ₁(V), 8.9 for ¹ E(V-R), 9.55 for ¹ E(3d-R), 6.98 for ³ A ₁(_V), 7.27 for ³ E(V), 7.82 for ³ A ₂(V), 8.30 for ³ E(3p-R), and 9.5 for ³ E(3d-R), where V and R refer to valence or Rydberg character. The results are compared with experimental excitation energies, previous ab initio studies of borazine, and with recent ab initio studies of benzene.Dedicated to Professor Dr. H. Hartmann on the occasion of his 65th birthday.     

Die Kristallstruktur der Mangansilicide im Bereich von MnSi∼1.7

Zusammenfassung MnSi_1.7-Einkristalle wurden nach demCzochralski-Verfahren gezüchtet. Mit Hilfe vonWeissenberg-Aufnahmen konnte das Mn-Defektsilicid Mn₂₇Si₄₇ identifiziert werden.

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Crystal structure of manganese silicides with MnSi_1.7 stoichiometry

Single crystals of MnSi_1.7 have been grown usingCzochralski's method. The Mn-defect silicid Mn₂₇Si₄₇ could be identified by means ofWeissenberg photographs.

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Relativistic perturbation theory of molecular structure

Summary The recently developed relativistic double perturbation theory is extended to handle relativistic changes of molecular structure more easily. This is achieved by simple coordinate scalings. Accurate higher order mixed perturbation energies for H ₂ ⁺ are calculated. The relativistic changes of bond energy,DE, of bond length,R _e , and especially of force constant,k, and of anharmonicity,a, are large, up to 100%·(Z/c)². The dominant contributions tok anda are due to the indirect change of the nonrelativistick anda connected with the relativistic change of bond length. Accordingly the relativistic changes obey Badger's and Gordy's rules (–RDEk).Dedicated to Prof. Klaus Ruedenberg in appreciation of his fundamental contributions to both formal theory and physical explanations in quantum chemistry     

Chromium(III) and oxovanadium (IV) complexes of some urea derivatives

Summary The preparation of eight new complexes of Cr^III and VO^IV with urea derivatives is reported here. The ligands used were 2-imidazolidinone (ethyleneurea, EU),N,N'-dimethyl-2-imidazolidinone (N,N -dimethylethyleneurea, DMEU), 2-imidazolidinethione (ethylenethiourea, ETU), andN, N, N, N -tetramethyl-2-imidazolidone (tetramethylurea, TMU). The previously reported complex VOCl₂(TMU)₂ was also prepared. All nine complexes were investigated with regard to conductimetry as well as visible and i.r. spectroscopy. All carbonyl-containing complexes exhibit a metal-oxygen bond, whereas in ETU complexes a metal-nitrogen bond seems to be favoured.     

New cobalt trimethylacetate complexes with pyridine

The reaction of the tetranuclear trimethylacetate complex Co₄(₃-OH)₂(-OOCCMe₃)₄(²-OOCCMe₃)₂(EtOH)₆ with pyridine in acetonitrile was studied. Two new compounds, viz., the hexanuclear cobalt(ii) complex Co₆py₄(₃-OH)₂(-OOCCMe₃)₁₀ (25% yield) and the unusual ionic compound [Co₃py₃(₃-O)(-OOCCMe₃)₆]⁺[Co₄py(₄-O)(-OOCCMe₃)₇]^– (5% yield), were prepared. The structures of the new compounds were established by X-ray diffraction analysis.     

Role of metal center in reactions of polynuclear nickel(ii) and cobalt(ii) trimethylacetates with 8-amino-2,4-dimethylquinoline

The reactions of 8-amino-2,4-dimethylquinoline (L) (1) with polynuclear nickel(ii) and cobalt(ii) hydroxotrimethylacetato complexes under anaerobic conditions were studied. The nonanuclear cluster Ni₉(₄-OH)₃(₃-OH)₃(_n-OOCCMe₃)₁₂(HOOCCMe₃)₄ gave the mononuclear complex Ni(²-L)(²-OOCCMe₃)₂ (2). The tetranuclear complex Ni₄(₃-OH)₂(-OOCCMe₃)₄(²-OOCCMe₃)₂(EtOH)₆ produced the mononuclear complex Ni(²-L)(²-OOCCMe₃)(OOCCMe₃)L (3). At room temperature, the cobalt-containing polynuclear trimethylacetates, viz., the polymer [Co(OH) _n (OOCCMe₃)_2–n ] _x and the tetranuclear complex Co₄(₃-OH)₂(-OOCCMe₃)₄(²-OOCCMe₃)₂(EtOH)₆, were transformed into the trinuclear cobalt(ii) complex Co₃(₃-OH)(-OOCCMe₃)₄(²-L)₂(OOCCMe₃) (4). Meanwhile, at 80 °C these compounds generated the binuclear cobalt(iii) complex Co₂(₂²-(HN)C₉NMe₂)₂(-OOCCMe₃)(L)(OOCCMe₃)₃ (5). The structures of the resulting compounds were established by X-ray diffraction analysis. Compounds 2—4 exhibit the antiferromagnetic spin-spin exchange coupling, whereas compound 5 is diamagnetic.     

Reactions of 1,4-difeffocenylbuta-1,3-diyne and 1,4-diphenylbut-l-en-3-yne with Ru3(CO)12. Crystal structure of Ru3(CO)8(μ3-η-1-η1-η4-η2-C4Ph2(CH=CHPh)2)

Diyne FcCmCC.CFc (Fc is ferrocenyl) reacts with Ru₃(CO)₁₂ in boiling hexane to yield binuclear complexes Ru₂ and Ru₂(CO)₆(C₄Fc₂(C=CFc)₂C=O) containing ruthenacyclopentadiene and diruthenacycloheptadienone rings, respectively. The isomerism of the complexes is due to the different ways of coupling of the alkyne fragments of the diyne, namely, head-to-head, head-to-tail or tail-to-tail. The reaction of enyne PhC=CCH=CHPh with Ru₃(CO)₁₂ under similar conditions gives isomeric binuclear complexes Ru₂(CO)₆(C₄Ph₂(CH=CHPh)₂) and trinuclear clusters Ru₃(CO)₆(w-CO)₂(C₄Ph₂(CH=CHPh)₂) and Ru₃(CO)₈(₃-,¹-¹-⁴-² C₄Ph₂(CH=CHPh)₂). The structure of the latter was determined by X-ray diffraction analysis. The Ru₃ triangle coordinates eight terminal CO groups and the organic ligand resulting from the head-to-head dimerization of enyne molecules; the ruthenacyclopentadiene moiety is ⁴-coordinated to the Ru(CO)₂ group, and the third ruthenium atom is 2-bound to one of the PhCH=CH groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1261–1267, May, 1996.     

Fluorimetric determination of beryllium with 4-methyl-6-acetyl-7-hydroxycoumarin

Summary The acid dissociation constant of 4-methyl-6-acetyl-7-hydroxycoumarin, as determined by spectrophotometry was found to be K_a=9.77×10^–9. Beryllium reacts with this reagent to form a water-insoluble complex that can be extracted into benzene. The maximum wavelengths of the excitation and emission spectra of the beryllium complex in benzene are 403 and 465 nm, respectively. Beryllium can be determined in the range 0.0050.1 g per 10 ml benzene when extracted from the solution at pH 7.57.8 into benzene.     

Isotopic hydrogen exchange in 1- and 2-aryl-5-methyltetrazoles

The rate constants for basic deuterium exchange of the methyl group (k_D) in 2-phenyl-5-methyl-tetrazole (I) and 1-aryl-5-methyltetrazole (II) and its derivatives with a polar substituent (R) in the phenyl ring were measured. The increased CH acidity of II as compared with I [k_D(II)/k_D(I)20] is in agreement with the calculated and experimental values regarding the character of the electron-density distribution in the molecules. The effect of R on the rate of deuterium exchange of the methyl group correlates with the ° constants (=3.0, r = 0.997). The results of measurement of the kinetic isotope effect during deuterium (tritium) exchange in II (k_D/k_T1.8) are discussed in connection with the peculiarities of the stepwise reaction mechanism.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No.1, pp. 127–130, January, 1978.     

Ionic Mobility, Phase Transitions, and Electric Conductivity in Ammonium Tetrafluoroantimonate and Heptafluorodiantimonate(III)

The dynamics of the fluoride and proton sublattices and the electrophysical properties of NH₄SbF₄ (I) and NH₄Sb₂F₇ (II) in the temperature range 210-435 K were studied by ¹⁹F and ¹H NMR and impedance spectroscopy. Types of ionic motion were determined and their activation energies were estimated. The structural phase transitions in I and II form the high-temperature modifications -NH₄SbF₄ and -NH₄Sb₂F₇, having high ionic (superionic) conductivity in the range 425-435 K (1.9-1.5×10^-3 S/cm).