New silanediamide complexes of rare-earth elements are synthesized: [Dy(Me2Si(NMes)2)(THF)22(μ-Cl)2] (Dy1), [Ln(Me2Si(NMes)2)(THF)22(μ-BH4)2] (Ln2, Ln = Y, Dy), and [Ln(Me2Si(NMes)2)(THF)22 (μ-SPh)2] (Ln3, Ln = Y, Tb, Dy), Mes = 2,4,6-(CH3)C6H2=mesityl. The compounds are isolated as crystalline phases Dy1, Ln2 (Ln = Y, Dy), Y3·2THF, Tb3·2C7H8, Dy3·2THF, and Dy3·2C7H8 and characterized by single crystal X-ray diffraction. All complexes have a binuclear structure; a silanediamide ligand is chelated to each Ln atom, and Cl–, BH_4^- , or SPh– act as bridges. By photoluminescence spectroscopy of the solutions of Tb and Dy complexes in THF it is shown that (Me2Si(NMes)2)2– is an effective ligand antenna, which sensitizes metal-centered emission of these lanthanides.

Синтезированы новые силандиамидные комплексы редкоземельных элементов: [{Dy(Me2Si(NMes)2)(thf)2}2(μ-Cl)2] (Dy1), и [{Ln(Me2Si(NMes)2)(thf)2}2(μ-BH4)2] (Ln2, Ln = Y, Dy) и [{Ln(Me2Si(NMes)2)(thf)2}2(μ-SPh)2] (Ln3, Ln = Y, Tb, Dy), Mes = 2,4,6-(CH3)C6H2 = мезитил. Соединения были выделены в виде кристаллических фаз Dy1, Ln2 (Ln = Y, Dy), Y3·2thf, Tb3·2C7H8, Dy3·2thf и Dy3·2C7H8 и охарактеризованы методом РСА. Все полученные комплексы имеют биядерное строение; к каждому атому Ln хелатно координирован силандиамидный лиганд, а мостиковыми выступают Cl–, BH4– или SPh–. С помощью фотолюминесцентной спектроскопии растворов комплексов Tb и Dy в ТГФ показано, что (Me2Si(NMes)2)2– является эффективным лигандом-антенной, который сенсибилизирует металл-центрированную эмиссию этих лантаноидов.

New silanediamide complexes of rare-earth elements are synthesized: [{Dy(Me2Si(NMes)(2))(THF)(2)}(2)(mu-Cl)(2)] (Dy1), [{Ln(Me2Si(NMes)(2))(THF)(2)}(2)(mu-BH4)(2)] (Ln2, Ln = Y, Dy), and [{Ln(Me2Si(NMes)(2))(THF)(2)}(2) (mu-SPh)(2)] (Ln3, Ln = Y, Tb, Dy), Mes = 2,4,6-(CH3)C6H2=mesityl. The compounds are isolated as crystalline phases Dy1, Ln2 (Ln = Y, Dy), Y32THF, Tb32C(7)H(8), Dy32THF, and Dy32C(7)H(8) and characterized by single crystal X-ray diffraction. All complexes have a binuclear structure; a silanediamide ligand is chelated to each Ln atom, and Cl-, BH4-, or SPh- act as bridges. By photoluminescence spectroscopy of the solutions of Tb and Dy complexes in THF it is shown that (Me2Si(NMes)(2))(2-) is an effective ligand antenna, which sensitizes metal-centered emission of these lanthanides.

The complex [Tb(Me2Si(NMes)2)(thf)22(μ-BH4)2] (1) has been synthesized by the reaction of [Tb(Me2Si(NMes)2)(thf)22(μ-Cl)2] (4; Mes is mesityl) with an excess of NaBH4 in THF. It has turned out that the complete replacement of the chloride ligands by BH4− occurs after heating the reaction mixture at 70°C for two weeks. When the reaction was stopped after five and seven days, polycrystalline [Tb(Me2Si(NMes)2)(thf)22(μ-BH4)x(μ-Cl)2 – x] phases (x ⁓ 1.2 (2); 1.4 (3)), as well as single crystals corresponding to these compositions, were isolated. The structures of 1–3 have been determined by single-crystal X-ray diffraction. The photoluminescent properties of solutions of these complexes in THF have been studied. The study demonstrates that the substitution of BH_4^ - for Cl– leads to an increase in the luminescence quantum yield.

The complex [{Tb(Me2Si(NMes)(2))(thf)(2)}(2)(mu-BH4)(2)] (1) has been synthesized by the reaction of [{Tb(Me2Si(NMes)(2))(thf)(2)}(2)(mu-Cl)(2)] (4; Mes is mesityl) with an excess of NaBH4 in THF. It has turned out that the complete replacement of the chloride ligands by BH4- occurs after heating the reaction mixture at 70 degrees C for two weeks. When the reaction was stopped after five and seven days, polycrystalline [{Tb(Me2Si(NMes)(2))(thf)(2)}(2)(mu-BH4)(x)(mu-Cl)(2 -) (x)] phases (x similar to 1.2 (2); 1.4 (3)), as well as single crystals corresponding to these compositions, were isolated. The structures of 1-3 have been determined by single-crystal X-ray diffraction. The photoluminescent properties of solutions of these complexes in THF have been studied. The study demonstrates that the substitution of BH4- for Cl- leads to an increase in the luminescence quantum yield.

The complex [Tb(Me 2 Si(NMes) 2 )(thf) 2 2 (μ-BH 4 ) 2 ] ( 1 ) has been synthesized by the reaction of [Tb(Me 2 Si(NMes) 2 )(thf) 2 2 (μ-Cl) 2 ] ( 4 ; Mes is mesityl) with an excess of NaBH 4 in THF. It has turned out that the complete replacement of the chloride ligands by BH 4 − occurs after heating the reaction mixture at 70°C for two weeks. When the reaction was stopped after five and seven days, polycrystalline [Tb(Me 2 Si(NMes) 2 )(thf) 2 2 (μ-BH 4 ) x (μ-Cl) 2 – x ] phases ( x ⁓ 1.2 ( 2 ); 1.4 ( 3 )), as well as single crystals corresponding to these compositions, were isolated. The structures of 1 – 3 have been determined by single-crystal X-ray diffraction. The photoluminescent properties of solutions of these complexes in THF have been studied. The study demonstrates that the substitution of BH_4^ - for Cl – leads to an increase in the luminescence quantum yield.

With the aim of designing new heteroorganic ligands capable of sensitizing the metal-centered photoluminescence (PL) of YbIII through the redox mechanism, a new diselenide, 2,2′-(diseleno-2,1-diphenylene)bis[benzothiazole] ((SeSN)2, 1), was synthesized and structurally characterized. The selenophenolate complexes Na(SeSN)(DME)2(2) and Yb(SeSN)3·0.5 THF (3) were synthesized by the reactions of diselenide 1 with Na and Yb metals in liquid ammonia. Complex 2 showed intense PL at 77 K in a DME solution, which appears as a broad band with a maximum at 575 nm assigned to the phosphorescence of the organoselenide ligand. In the crystalline state, ytterbium complex 3, which was isolated and structurally characterized as an adduct with THF, exhibited intense metal-centered PL in the 980–1100 nm region. This PL is observed upon direct excitation or upon excitation through SeSN ligands (250–380 nm), as well as through excitation of the ligand-to-metal charge transfer (LMCT) band in the 430–700 nm region. The presence of low-energy LMCT states capable of sensitizing the metal-centered PL of YbIII in complexes with organoselenide ligands is responsible for a significant reduction of the Stokes shift of luminescence and opens up new prospects for the development of lanthanide-containing infrared luminophores exhibiting luminescence under long-wavelength excitation.

Синтезированы новые силандиамидные комплексы двухвалентных лантаноидов с разным отношением металл-лиганд: K[K(thf)][Yb(Me2Si(NMes)2)2] (1) и [Eu2(Me2Si(NMes)2)2(thf)3] (2) (Mes = 2,4,6-(CH3)C6H2 = мезитил). Соединения были выделены в виде кристаллических фаз 1 и 2∙C7H8 и охарактеризованы методом РСА. Соединение 1 представляет собой «атный» комплекс, в котором два силандиамидных лиганда координируются к Yb хелатным способом атомами азота, а ионы калия связаны с ароматическими кольцами Mes-заместителей. В биядерном комплексе 2 наблюдаются два типа координации силандиамидных лигандов: μ-κ1N,κ2N и μ-κ2N,κ2N.

New silanediamide complexes of divalent lanthanides with different metal-to-ligand ratios are synthesized: K[K(THF)][Yb(Me2Si(NMes)2)2] (1) and [Eu2(Me2Si(NMes)2)2(THF)3] (2) (Mes = 2,4,6-(CH3)C6H2 == mesityl). The compounds are isolated as crystalline phases 1 and 2·C7H8 and characterized by single crystal X-ray diffraction. Compound 1 is an ate complex in which two silanediamide ligands are coordinated to Yb by nitrogen atoms in a chelate manner, and the potassium ions are linked with aromatic rings of mesityl substituents. In binuclear complex 2, two coordination types of the silanediamide ligand are observed: μ-κ1N,κ2N and μ-κ2N,κ2N.

Федеральное государственное бюджетное учреждение наукиИнститут неорганической химии им.А. В. Николаева Сибирского отделения Российской академии наук

Binuclear complexes [Fe2(µ-S2ER2)(CO)6] (ER2 = SiMe2 (Iа), SiEt2 (Ib), SnEt2 (Ic)), promising precursors of heterometallic clusters, were synthesized. Reactions of these complexes with transition metal halide complexes, [Cp"RhCl2]2 (Cp" = η5-C5H3tBu2), [(Dppe)NiCl2] (Dppe = Ph2PCH2CH2PPh2), [(Ph3P)AuCl], and [Mn(CO)5Cl], were studied. The reactions gave heterometallic clusters [Fe2Rh(µ3-S)2(CO)6Cp"] (II), [Fe2Ni(µ3-S)2(CO)6(Dppe)] (III), [Fe2(CO)6(µ-SSnClEt2)(µ-SAu(PPh3))] (IV), [Fe2(CO)6(µ4,η2-S2SnEt2){Mn(CO)4Cl}2] (V), and [Fe2Mn(CO)9Mn(CO)5(µ3-S)(µ4-S)] (VI). Cluster V was found to be converted to VI upon photochemical activation. The structures of compounds I–VI were determined by X-ray diffraction (CIF file CCDC nos. 751214 (Ic), 751215 (III·0.5C7H8), 2062206 (V), 2062207 (Ib), 2062208 (Ia), 2062209 (IV·0.5CH3C5H9).

A new polymorph of the β-modification of N,N′-di(pyridin-2-yl)formamidine that is more thermodynamically stable than the known α-modification is obtained. The crystal of β-modification contains hydrogen bonded molecular dimers with a skewed geometry. Therefore, the space group is not centrosymmetric – P42. This geometry is a result of the molecular E-syn,syn conformation in crystals of the β-phase, which differs from the E-anti,syn conformation in the α-phase. The number of crystallographically non-equivalent molecules (8) in the β-modification is unusually large for organic compounds. The structure of the packing is analyzed, and it is shown that the centers of dimers follow the sites of a distorted body-centered cubic pseudo-lattice (Ат ≈ 10 Å, αт = 90°) with a 16 times decreased unit cell volume. Reasons for symmetry violations causing modulations are considered.

Взаимодействием [Er(N(SiMe3)2)3] с HN3Dipp ((N3Dipp)– = N,N'-1,3-бис(2,6-диизопропилфенил)триазенид) получены комплексы [Er(N3Dipp)(N(SiMe3)2)2] (1) и [Er(N3Dipp)2(N(SiMe3)2)] (2). Реакция 2 с тиофенолом приводит к образованию комплекса [Er(N3Dipp)2(SPh)(THF)] (3). Строение соединений установлено методом рентгеноструктурного анализа на монокристаллах следующих твердых фаз: 1, 2·C6H6 и 3.

Получена новая полиморфная β-модификация N,N'-ди(пиридин-2-ил)формамидина, более термодинамически стабильная по отношению к известной α-модификации. В кристалле β-модификации присутствуют связанные парной водородной связью димеры молекул, имеющие скрученную геометрию, поэтому пространственная группа нецентросимметрична — P42. Такая геометрия — следствие реализации E-син,син конформации молекулы в кристаллах β-фазы, отличающейся от E-анти,син конформации в α-фазе. Число кристаллографически неэквивалентных молекул (8) в β-модификации необычно большое для органических соединений. Проведен анализ упаковки структуры, показано, что центры димеров следуют узлам искаженной объемно-центрированной кубической псевдорешетки (Ат ≈ 10 Å, αт = 90°) с уменьшенным в 16 раз объемом примитивной ячейки. Рассмотрены причины нарушения симметрии, приводящие к появлению модуляции.

By the interaction of [Er(N(SiMe3)2)3] with HN3Dipp ((N3Dipp)– = N,N′-1,3-bis(2,6-diisopropylphenyl) triazenide) [Er(N3Dipp)(N(SiMe3)2)2] (1) and [Er(N3Dipp)2(N(SiMe3)2)] (2) complexes are obtained. The reaction of 2 with thiophenol gives [Er(N3Dipp)2(SPh)(THF)] complex (3). The structures of the compounds is determined by single crystal Xray diffraction of the following solid phases: 1, 2·C6H6, and 3.

Синтезированы новые кластеры железа [Fe3(μ3-Q)(μ3-AsN(i-Bu)2)(CO)9] (Q = Se (1a), Te (1b)). Изучены реакции гидролиза этих соединений, приводящие к разрыву связи As—N. Строение кластеров 1a,b и продуктов гидролиза [Fe6(μ6,η2-AsOAs)(μ3-Te)2(CO)18] (2), [NH2(i-Bu)2][Fe3(μ3-Se)(μ3-AsO)(CO)9] (3) и [{Fe3(μ3-Se)(μ4-As)(CO)9}2{Fe2(μm2-Se)2·(CO)5}] (4) установлено методом рентгеноструктурного анализа.