Complexes of Co(II), Ni(II), Zn(II), and Cu(II) perchlorates and hexafluorophosphates with 4′-(4″-benzo-15-crown-5)oxy-2,2′:6′,2″-terpyridine (L) [M(L) 2 ](ClO 4 ) 2 · 3H 2 O and [M(L) 2 ](PF 6 ) 2 · 2H 2 O were synthesized. The spectral criteria of ligand coordination through the terpyridine nitrogen atoms were established. An assumption concerning the benzo-15-crown-5 conformation in the ligand molecule in the synthesized complexes was made. The extraction and ion-selective properties of L were studied.

Complexes of 4′-(4′″-benzo-15-crown-5)methyloxy-2,2′:6′,2″-terpyridine (L) with metal perchlorates and hexafluorophosphates, [ML2](ClO4)2 · nH2O and [ML2](PF6)2 · nH2O · mC2H5OH (M = Ni(II), Co(II), Zn(II), Cu(II); n = 0–3; m = 0–2), were synthesized. Their vibrational spectra were studied. The spectral criteria for ligand coordination through the terpyridinic nitrogen atoms were established. The conformational structure of the B15C5 macrocycles of a ligand molecule in the synthesized complexes was proposed. The complexes were studied by thermogravimetry.

Синтезированы комплексные соединения 4-(4-бензо-15-краун-5)-метилокси-2,2:6,2-терпиридина (L) с перхлоратами и гексафторофосфатами металлов состава [ML2](ClO4)2 · nH2O и [ML2](PF6)2 · nH2O · mC2H5OH (М = Ni(II), Сo(II), Zn(II), Cu(II); n = 0–3; m = 0–2). Изучены их колебательные спектры. Установлены спектральные критерии координации лиганда через терпиридиновые атомы азота. Высказано предположение о конформационном строении макроциклов Б15К5 молекулы лиганда в синтезированных комплексах. Проведено термогравиметрическое исследование полученных комплексных соединений.

The synthesis of 4′-(4‴-benzo-15-crown-5)-methyloxy-2,2′:6′,2″-terpyridine (L) and is complexes with cobalt(II) and zinc(II) [CoL 2 ](ClO 4 ) 2 · 3H 2 O ( I ) and [ZnL 2 ](ClO 4 ) 2 · 3H 2 O ( II ) was described. For L and its complexes, the parameters of electronic absorption spectra in acetonitrile were determined and 1 H NMR signals were assigned. The structures of I and II were determined by X-ray crystallography. Compounds I and II are isostructural and consist of complex cations [ML 2 ] 2+ (M = Co, Zn), ClO 4 − anions, and crystal water molecules. The M atoms are located in special positions on twofold axes. The M atoms are surrounded by six N atoms of the terpyridine moieties of two organic molecular ligands. The M-N distance for the N(2) atoms of the central rings of the terpyridine moieties in both structures is shorter than for the side rings. The coordination polyhedra of the M atoms can be described as severely distorted octahedra. The major distortion of the octahedra is that the N…N distances in a terpyridine moiety are considerably shorter than those between the atoms of different moieties. The maximal deviation of the terpyridine atoms from the mean-square planes through these atoms is observed for the C(2) atom: 0.103(3) and 0.106(4) Å in I and II , respectively. The Co(1) and Zn(1) atoms are at a distance of, respectively, 0.1682(14) and 0.1415(17) Å from the corresponding planes.

Описан синтез 4-(4-бензо-15-краун-5)-метилокси-2,2:6,2-терпиридина (L) и его комплексных соединений с кобальтом(II) и цинком(II) состава [СоL2](ClO4)2 · 3H2O (I) и [ZnL2](ClO4)2 · 3H2O (II). Для L и его комплексов определены параметры ЭСП в ацетонитриле, проведено отнесение сигналов протонов в спектрах ЯМР 1. Для I и II проведен РСА. Соединения I и II изоструктурны и состоят из комплексных катионов [ML2]2+ (M = Co, Zn), анионов и молекул кристаллизационной воды. Атомы M находятся в частных позициях на двойных осях. Окружение атомов M составляют шесть атомов N терпиридиновых фрагментов двух органических молекулярных лигандов. Расстояние M–N для атомов N(2) центральных колец терпиридиновых фрагментов в обеих структурах меньше, чем для боковых. Координационные полиэдры атомов M можно описать как сильно искаженные октаэдры. Основное искажение октаэдров заключается в том, что расстояния N···N в одном терпиридиновом фрагменте значительно короче, чем между атомами разных фрагментов. Максимальное отклонение атомов терпиридиновых фрагментов от проведенных через них среднеквадратичных плоскостей для атома C(2) составляет 0.103(3) и 0.106(4) A в I и II соответственно. Атомы Co(1) и Zn(1) находятся на расстояниях 0.1682(14) и 0.1415(17) A от соответствующих плоскостей.

First calculation of molecular parameters (MP) of new octa-(benzo-15-crown-5)-substituted phthalocyanine derivatives and of its metallo complexes Zn(II), Ni(II) ( Ib, Ic ) is carried out. A prediction was made of the possible formation therefrom of metaphases, and for that purpose the synthesis of these compounds and investigation of their mesomorphic properties was performed. For compounds Ia-Ic the formation of high-temperature enantiotropic mesophases was established typical for discotic mesogenes, in good agreement with the prediction. Proceeding from the data on miscibility of 2,3,9,10,16,17,23,24-octa-[(4′-benzo-15-crown-5)-oxy]-phthalocyanine Ia with discotic mesogene 2,3,6,7,10,11-hexa(cyclohexanebenzoyloxy)triphenylene ( II ) displaying nematic mesomorphism the compound Ia was assigned to the group of nematic mesogenes and by the texture of the mixture to discotic mesogenes forming columnar type nematic phase ( N Col ). Convergence of the results of prediction and experimental data is about 83%.

Octa(benzo-15-crown-5)-substituted phthalocyanine and its complexes with d-metals (NiII, CoII, CuII, ZnII, and CdII) have been synthesized for the first time. The compounds were studied by UV—Vis spectroscopy, MALDI-TOF mass spectrometry, NMR, ESR, IR spectroscopy, and Raman spectroscopy. The dependence of the spectral characteristics of the studied compounds on the ion radius of the complexing agent was demonstrated.

Calculation and analysis of molecular parameters (MP) phthalocyanine metallocomlexes (Cu, Cd, Co, La, Lu, Ru and Y), including crown ether fragments was carried out. It is established, that the given complexes are inclined to mesomorphism inherent to disc-like mesogenes.Three (Cu, Cd and Co) from seven metallocomplexes are synthesized and thermotropic mesomorphism of individual compounds and their mixes with chiral nematic cholesterol diphenylate has been investigated. It was revealed, that copper and cobalt phthalocyanines possess latent mesomorphism. Convergence of prognostication results with experimental data amount to 83 %.

A new method of synthesis of the lariat crown ether 1,4,10,13-tetraoxa-7,16-diaza(diphenylmethyl)cyclooctadecane (L) has been described. The sodium thiocyanate complex with L [NaL](NCS) has been studied by X-ray crystallography, and the major vibrational frequencies in its IR spectrum have been assigned. The crystals of the complex are monoclinic: a = 11.538(2) Å, b = 9.796(2) Å, c = 7.564(2), Å, β = 90.38(3)°, Z = 2, space group P 2 1 / c , R 1 = 0.0486 for 1733 reflections with I > 2σ( I ). The compound has an ionic structure. In the centrosymmetric cation [NaL] + , both the macrocyclic part and the side groups of the ligand L are involved in coordination with the metal atom. The coordination polyhedron of the Na atom is a hexagonal bipyramid in which the equatorial plane is formed by six donor atoms of the substituted diaza-18-crown-6 ether (DA18C6) (av. Na-O ether , 2.682 Å; Na-N, 2.861 Å). The phosphoryl oxygen atoms of the side chains of the ligand occupy the axial positions (Na-O P , 2.325 Å). It is demonstrated that the cationic complexes of L can be, in principle, used as components of supramolecular machines.

Cation-induced dimerization of nickel(II), platinum(II), and palladium(II) meso -tetra(benzo-15-crown-5)porphyrinates (Ni(II)TCP, Pd(II)TCP, and Pt(II)TCP) on treatment with potassium thiocyanate in a chloroform-methanol solution has been studied by electronic absorption spectroscopy. The formation of [{MTCP} 2 (K + ) 4 ](SCN − ) 4 in solution induces a hypsochromic shift of the Soret band and a bathochromic shift of the β-band with respect to their positions in the spectrum of MTCP. The equilibrium constants ( K ) for the 2MTCP + 4K + = [{MTCP} 2 (K + ) 4 ] processes at 20°C are determined to be as follows: log K Ni(II)TCP = 27.31 ± 1.67, log K Pd(II)TCP = 27.16 ± 1.43, and log K Pt(II)TCP = 26.15 ± 1.56.

The reactions of meso-tetra(benzo-15-crown-5)porphyrin with platinum(II) and palladium(II) chlorides were studied. Palladium(II) and platinum(II) meso-tetra(benzo-15-crown-5)porphyrinates were isolated and studied by H-1 NMR and electronic absorption spectroscopy. The structures of the compounds were identified by comparative analysis of their spectral properties and those of the starting meso-tetra(benzo- 15 -crown-5)porphyrin.

The oxidation of platinum(II) and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates by molecular chlorine and hydrogen peroxide in a medium of hydrochloric acid was studied. The corresponding platinum(IV) and palladium(IV) dichloro-meso-tetra(benzo-15-crown-5)porphyrinates were isolated and characterized by H-1 NMR and electronic absorption spectroscopy.