The reaction of 1,3-diketone containing 1-methyl-1H-pyrazol-4-yl and perfluoropropyl fragments with TbCl3·6H2O in the presence of NaOH in ethanol is studied. The molecular and crystal structures of the complex are studied by single-crystal X-ray diffraction (XRD). Compound [Tb(L)3(EtOH)2] crystallizes in the triclinic crystal system with the space group P1̅ . The geometry of the coordination polyhedron LnO8 corresponds to a square antiprism. Intermolecular interactions N…H–O, C–H…O, and C–H…F leading to the formation of supramolecular chains are observed in crystals of the complex. The UV-irradiated complex exhibits green luminescence caused by transitions 5D4 → 7Fj (j = 2–6) characteristic of the Tb3+ ion. The main photophysical luminescence parameters are determined, and the scheme of energy transfer in the complex is proposed. The synthesized compound can be of interest as an independent luminophore or as the initial substance for the synthesis of heteroligand complexes by the substitution of ethanol molecules in the internal coordination sphere.

Получена серия молекулярных соединений и координационных полимеров Zn2+, Mn2+ Cd2+, а также Eu3+ и Tb3+ с анионами 4-аллил-2,3,5,6-тетрафторбензойной кислоты (4-Afb) и 1,10-фенантролином состава [Zn(H2O)(phen)(4-Afb)2] (1), [Mn(H2O)(phen)(4-Afb)2]n·nH2O (2), [Cd(H2O)(phen)(4-Afb)2]n (3), [Cd(phen)(4-Afb)2]n (4), [Ln2(phen)2(4-Afb)6] (Ln = Eu 5Eu; Tb 5Tb). Показано, что в зависимости от условий кристаллизации происходит формирование координационных полимеров кадмия различного состава и строения. Синтезированные соединения охарактеризованы методами РСА, РФА, ИК-спектроскопии и CHN-анализа. Нековалентные взаимодействия проанализированы с использованием анализа поверхностей Хиршфельда. Выявлено, что основной вклад в стабилизацию кристаллических упаковок вносят π··· π, C–H···F, C–F···π взаимодействия. Также были исследованы фотолюминесцентные свойства для комплексов 5Eu и 5Tb. Показана перспективность использования структурообразующих эффектов нековалентных взаимодействий типа «арен-перфторарен» для предорганизации в кристалле реакционноспособных функциональных групп.

Получена серия бис -циклометаллированных комплексов иридия(III) с различными 2-арил-1-бензилбензимидазолами (арил = 4-хлорфенил, 4- трет -бутилфенил, 3,4-диметоксифенил) и 4,4'-дикарбокси-2,2'-бипиридином. Синтезированные комплексы изучены методами спектроскопии ЯМР 1 H, масс-спектрометрии высокого разрешения, рентгеноструктурного анализа, спектрофотометрии, люминесцентной спектроскопии и циклической вольтамперометрии. В электронных спектрах комплексов полосы поглощения претерпевают заметный батохромный сдвиг при увеличении электронодонорных свойств бензимидазольного лиганда. В растворе комплексы обладают фотолюминесценцией в желто-красной области спектра с квантовым выходом в интервале 0.4–7.7% и временем жизни возбужденного состояния в диапазоне 71–408 нс. По данным циклической вольтамперометрии, в растворах изученных комплексов наблюдаются квазиобратимые редокс-переходы ( E ox = 1.16–1.57 В отн. СВЭ, ацетонитрил).

It was shown that refluxing of europium(III) acetate hydrate with trifluoroacetic acid in a dioxane–acetonitrile mixture gives the polymer {[Eu(μ-OOCCF 3 ) 3 (OH 2 ) 2 ]} n ( I ) containing dioxane solvate molecules. The reaction of I with [phen(µ-OOC t Bu) 2 (OOC t Bu) 2 ] ( II ) (phen = 1,10-phenanthroline) in CH 2 Cl 2 at room temperature gives a precipitate, the recrystallization of which from acetonitrile affords an unusual trinuclear heterometallic heteroanionic phen 2 Zn 2 Eu(µ 3 -OH)(OOC t Bu) 4 (OOCCF 3 ) 2 complex ( III ). The structure of the products was established from X-ray diffraction data (CCDC no. 2235937–2235939). The optical properties of complex III were studied.

It has been shown that boiling aqueous europium(III) acetate with trifluoroacetic acid in a dioxane-acetonitrile mixture leads to the formation of a polymer {[Eu(μ-OOCCF3)3(OH2)2]}n (I) containing solvate dioxane molecules. The interaction of I in CH2Cl2 with [Phen2Zn2(µ-OOCBut)2(OOCBut)2] (II) at room temperature forms a precipitate, recrystallization of which from acetonitrile gives an unusual trinuclear heterometallic heteroanionic complex Phen2Zn2Eu(µ3-OH)(OOCBut)4(OOCCF3 )2 (III). The structure of the obtained compounds was established according to X-ray diffraction data (CCDC No. 2235937-2235939). The optical properties of complex III were studied.

New complex [RuL(Dmdcbp)2]PF6 (I) is synthesized by the consecutive reactions of [Ru-p-cymene]2Cl4 with 3,3',5,5'-tetramethyl-1,1'-biphenyl-4,4'-bipyrazole (L) and 4,4'-dicarboxy-2,2'-bipyridine in a methanol–chloroform medium. The composition of complex I is confirmed by NMR and elemental analysis, and the optical and luminescence properties of the complex are studied. Ligand L is characterized for the first time by X-ray diffraction (CIF file CCDC no. 2118676). Quantum chemical calculations in terms of the density functional theory are performed for the interpretation of the absorption and emission spectra. Complex I is promising for using as a photosensitizer.

The use of dicyanamide and chelating phenanthroline ligands resulted in the synthesis of organometallic europium and neodymium coordination polymers [Ln(Phen) 2 {N(CN) 2 } 3– x Cl x (CH 3 OH)](CH 3 OH) y ] ∞ (Ln = Eu ( I ), Nd ( II )) in which the dicyanamide ligand forms 1D chains, while the phenanthroline ligand provides packing of the 1D polymer in the crystal lattice. Under similar conditions, the binuclear complex [Gd(Phen) 2 (μ-OH){N(CN) 2 }(H 2 O)] 2 Cl 2 ( III ) was obtained for gadolinium, with the dicyanamide ligands being coordinated to only one gadolinium ion without forming a polymer chain (CCDC CIF files nos. 1936378 ( I ), 1936379 ( II ), 1936377 ( III )).

The reactions of Cd(NO 3 ) 2 ∙ 4H 2 O and Eu(NO 3 ) 3 ∙ 6H 2 O with potassium salts of the benzoic acid derivatives and 2,2'-bipyridine (Bipy) in ethanol, under the same synthesis conditions, afford the homo- and heterometallic complexes: [Eu 2 Cd 2 (BA) 8 (NO 3 ) 2 (Bipy) 2 ] ( I , BA is benzoic acid anion), [Ln 2 Cd 2 (4-TBA) 10 (Bipy) 2 ] (Ln = Eu ( II ), Tb ( III ); 4-TBA is 4-(trifluoromethyl)benzoic acid anion), [Cd(4-CBA) 2 (H 2 O)(Bipy)] ( IV , 4-CBA is 4-cyanobenzoic acid anion), [Cd(PFBA) 2 (H 2 O)(Bipy)] n ( V , PFBA is pentafluorobenzoic acid anion), and [Cd 2 (4-APFBA) 4 (Bipy) 2 ] ∙ 4H 2 O ( VI , 4-ATFBA is 4-amino-2,3,5,6-tetrafluorobenzoic acid anion). The structures of new complexes I , II , IV , and VI are determined by X-ray structure analysis (CIF files CCDC nos. 1970348, 1970350, 1970347, and 1970351, respectively). The isostructural character of complexes II and III is confirmed by X-ray diffraction analysis. The structures and compositions of the series of isolated compounds I – VI are determined by the nature of substituents in the benzoate anion. The photoluminescence properties of compounds II and III are studied.

Complexes {[(Zn(Bbtm)(H2O)4](NO3)2}n (I) and [Cu(Вbtm)(NO3)2]n (II) are formed due to the reactions of solutions of zinc and copper(II) nitrates with the bis(1,1'-1,2,3-benzotriazolyl)methane ligand (Bbtm). Their crystal structures are determined by X-ray diffraction analysis (CIF files ССDС nos. 1963126 (I) and 1963127 (II)). Complex I is a linear metal-organic framework (1D-MOF) in which the octahedral coordination of the central atom is provided by four water molecules and two nitrogen atoms of two Bbtm molecules in the trans position. In the structure of complex II, the coordination sphere of copper contains two nitrogen atoms of the Вbtm ligands and four oxygen atoms of two nitrate anions, one of which is bridging like the Вbtm ligand. This makes it possible to describe the structure of complex II as 3D-MOF. The luminescence spectra are recorded for earlier undescribed compound I. The emission maximum is observed at 363 nm. Compound I is also tested as a catalyst for the cycloaddition of СО2 to epoxides. The synthesized MOF efficiently catalyzes the cycloaddition reactions for both monosubstituted and disubstituted epoxides.

The reactions of Cd(NO3)(2)center dot 4H(2)O and Eu(NO3)(3)center dot 6H(2)O with potassium salts of the benzoic acid derivatives and 2,2'-bipyridine (Bipy) in ethanol, under the same synthesis conditions, afford the homo- and heterometallic complexes: [Eu2Cd2(BA)(8)(NO3)(2)(Bipy)(2)] (I, BA is benzoic acid anion), [Ln(2)Cd(2)(4-TBA)(10)(Bipy)(2)] (Ln = Eu (II), Tb (III); 4-TBA is 4-(trifluoromethyl)benzoic acid anion), [Cd(4-CBA)(2)(H2O)(Bipy)] (IV, 4-CBA is 4-cyanobenzoic acid anion), [Cd(PFBA)(2)(H2O)(Bipy)](n)(V, PFBA is pentafluorobenzoic acid anion), and [Cd-2(4-APFBA)(4)(Bipy)(2)] center dot 4H(2)O (VI, 4-ATFBA is 4-amino-2,3,5,6-tetrafluorobenzoic acid anion). The structures of new complexesI,II,IV, andVIare determined by X-ray structure analysis (CIF files CCDC nos. 1970348, 1970350, 1970347, and 1970351, respectively). The isostructural character of complexesIIandIIIis confirmed by X-ray diffraction analysis. The structures and compositions of the series of isolated compoundsI-VIare determined by the nature of substituents in the benzoate anion. The photoluminescence properties of compoundsIIandIIIare studied.

Complexes {(NMe2H2)[Ln(TDA)(HCOO)] ∙ 0.5H2O)} are prepared by the solvothermal synthesis in a water–dimethylformamide (1 : 1) system from a mixture of 1,2,3-triazole-4,5-dicarboxylic acid (H3TDA), NaOH, and Ln(NO3)3 (Ln = Eu, Gd). The crystal structure of the europium complex is determined by X-ray structure analysis (CIF file CCDC no. 1939689). This compound is shown to be the ionic metal-organic framework, where the cavities in the anionic structure of [Eu(TDA)(HCOO)]– are partially occupied by the dimethylammonium cations and water molecules. The study of the luminescence spectra of the gadolinium derivative gives the energy of the triplet level of the H3TDA ligand (~25 300 cm–1), the value of which makes it possible to efficiently sensitize the luminescence of rare-earth metal ions, in particular, Eu3+. The decay kinetics and the emission and excitation spectra of the heterometallic derivatives {(NMe2H2)[Gd1 – xEux(TDA)(HCOO)] ∙ 0.5H2O)} are studied. The dilution of europium with gadolinium results in a substantial decrease in the concentration quenching of the europium luminescence and an increase in the observed lifetimes of the excited state of Eu3+.

New trinuclear Cd–Ln molecular complexes [EuCd 2 (O 2 CC 6 F 5 ) 6 (NO 3 )(Bipy) 2 ] ( I , Bipy is 2,2'-bipyridine) and [LnCd 2 (Bzo) 6 (NO 3 )(Phen) 2 ] · 4MeCN (Ln = Tb ( II) , Eu ( III ), Bzo is anion of 3,5-di- tert -butylbenzoic acid, Phen is 1,10-phenanthroline) are studied. Their structures are determined by X-ray structure analysis (СIF files CCDC nos. 1938125 ( I ), 1938124 ( II )) or by X-ray diffraction analysis ( III ), and the photoluminescence properties are studied. The reactions of complexes I and II with terephthalic acid (H 2 Bdc) are accompanied by the destruction of the heterometallic molecules to form 2D coordination polymers [Cd 3 (Bbdc) 3 (Bipy) 2 ] 3 n · 4 n MeCN · n H 2 O ( IV ) and [Cd 2 (Bdc) 2 (Phen) 2 ] n · 2 n DMF ( V ) (СIF files CCDC nos. 1938126 and 1937492, respectively).