In this study, we present a convenient and accessible synthesis of [M6X8(OCH3)6]2- clusters from [M6X8X6]2- (M = Mo, W; X = Br, I) using methanol and sodium hydroxide, without the use of absolute solvents or sodium methylate. The substitution of terminal methylate ligands in the clusters by pyrazolate ligands was conducted using a reaction in the melt of the organic ligand. The formation of anionic [M6X8(pz)6]2- (pz = pyrazolate) complexes was confirmed by both single crystal X-ray diffraction analysis and 1H NMR spectroscopy in solution. The complexes exhibited broadband emission in solid state with emission maxima ranging from 600 to 700 nm (depending on the cluster core) with quantum yields of approximately 7 %.

Chiral rhenium(I) emitters exhibiting circularly polarized phosphorescence (CPP) are an attractive mainstay for CP organic light-emitting diodes (CP-OLEDs). However, the efficiency of such emitters is not ideal, and they have never been explored for circularly polarized electroluminescence (CPEL) applications. Here, we have tailored robust chiral Re(I) complexes with improved CPP properties, and demonstrated CPEL from rhenium emitters for the first time. Two pairs of enantiomeric Re(I) complexes have been synthesized by introducing of one or two chiral menthol groups into 1,10-phenanthroline unit (phen) of archetypical emitters [ReBr(CO) 3 (phen)]. The designed complexes exhibit a yellow CPP with enhanced | g lum | factors (up to 2.5×10 −2 ) and a good quantum efficiency. The pioneering Re(I)-based CP-OLEDs (based on the obtained emitters) exhibit yellow CPEL with | g EL | factors of up to 6.2×10 −3 and a maximal external quantum efficiency of 13.2 %. This work highlights the good potential of chiral Re(I) emitters for CPEL applications, and opens up a new shortcut to CPP-active Re(I) complexes.

New luminescent cluster complex (Bu4N)2[W6I8(N3C6H4)6] (I) is obtained by the reaction of (Bu4N)2[W6I8(OOCCH3)6] with 1-trimethylsilyl-1,2,3-benzotriazole (Me3Si-N3C6H4) is obtained. The crystal structure is determined for cocrystallizate I with 1,2,3-benzotriazole (Bu4N)2[W6I8(N3C6H4)6]· ·4(N3C6H5) (I·4BTA). According to single crystal X-ray diffraction data, tungsten atoms of the W6I84+ cluster core are monodentate coordinated by N1 atoms of 1,2,3-benzotriazolate ligands (average W–N distance 2.20 Å). For the powder sample of I bright phosphorescence is revealed with the emission maximum at 640 nm, φ = 24

New complex of lead(II) with beta-diketonate ligand PbL2 is described, where L=CH3COCHCOC(OCH3)(CH3)2, 5-methoxy-5-methylhexan-2,4-dionate). Crystal structure of the compound has been determined and its thermal properties have been studied. Chains of 1D coordination polymers form crystals of the complex, where the molecules are connected through the chelate-bridging oxygen atoms, methoxy groups remain free and form hydrogen bonds between the chains. PbL2 sublimates at 120 degrees C under reduced pressure (P=10- 2 Torr) with partial decomposition. When heated in the condensed phase the complex decomposes with the formation of lead (II) oxide and evolution of a pyran derivative into gas phase. The mechanism of lead(II) complex thermolysis in support of the condensation of two ligands is discussed. A new organic product was identified by 13C and 1H NMR, IR and PL spectroscopy and mass spectrometry; the crystal structure of the product was determined.

An unprecedented cluster [Cu7I11]4- 7 I 11 ] 4- with a pseudo-C3 C 3-symmetric cage-like structure has been identified in an ionic salt with [1,4-(Ph3PCH2)2C6H4]2+ 3 PCH 2 ) 2 C 6 H 4 ] 2+ cations. The [Cu7I11]4- 7 I 11 ] 4- anion is composed of a six-point star Cu6(mu 6-I)(mu 2- 6 (mu 6-I)(mu 2- I)6 6 capped by a CuI4 4 tetrahedron. A Cu6 6 hexagonal subunit of [Cu7I11]4-exhibits 7 I 11 ] 4- exhibits strong Cu center dot center dot center dot Cu interactions (d Cu-Cu = 2.457-2.958 & Aring;) as evidenced by QTAIM analysis. At 25 degrees C, the new [Cu7I11]4- 7 I 11 ] 4- cluster emits a weak phosphorescence. In addition, two [Cu2I4]2- 2 I 4 ] 2- iodocuprates supported by [1,4-(Ph3PCH2)2(C6H4)n]2+ 3 PCH 2 ) 2 (C 6 H 4 ) n ] 2+ cations (n = 1 or 2) are reported, showing no Cu center dot center dot center dot Cu interactions.

An unprecedented cluster [Cu7I11]4– with a pseudo-C3-symmetric cage-like structure has been identified in an ionic salt with [1,4-(Ph3PCH2)2C6H4]2+ cations. The [Cu7I11]4– anion is composed of a six-point star Cu6(µ6-I)(µ2-I)6 capped by a CuI4 tetrahedron. A Cu6 hexagonal subunit of [Cu7I11]4– exhibits strong Cu∙∙∙Cu interactions (dCu–Cu = 2.457–2.958 Å) as evidenced by QTAIM analysis. At 25 °C, the new [Cu7I11]4– cluster emits a weak phosphorescence. In addition, two [Cu2I4]2– iodocuprates supported by [1,4-(Ph3PCH2)2(C6H4)n]2+ cations (n = 1 or 2) are reported, showing no Cu∙∙∙Cu interactions.

Mixed-ligand 2,2 '-bipyridine, 1,10-phenanthroline based copper(II) complexes are often considered as potential antitumor agents. This research was aimed at synthesis and finding the cytotoxic potential of copper(II) complexes with diphenylphosphinic acid (HL) and 2,2 '-bipyridine, 1,10-phenanthroline derivatives - [Cu(phen) (H2O)L2]& sdot;H2O (1), [Cu(dmphen)(H2O)L2] (2), [Cu(Cl-phen)(H2O)2L]L & sdot;EtOH (3), [Cu(bipy)(H2O)L2] (4) and Cu (dmbipy)(H2O)L2 (5) (phen - 1,10-phenanthroline, dmphen - 4,7-dimethyl-1,10-phenanthroline, Cl-phen - 5chloro-1,10-phenanthroline, bipy - 2,2 '-bipyridine, dmbipy - 4,4 '-dimethyl-2,2 '-bipyridine). Obtained mononuclear compounds have been characterized by EPR and IR-spectroscopy, elemental, thermogravimetric, singlecrystal and powder X-ray diffraction analyses. According to single-crystal X-ray diffraction data, complexes possess distorted trigonal bipyramidal or square pyramidal geometry. 2,2 '-Bipyridine and 1,10-phenanthroline derivatives have been shown to be chelating agents in these complexes, while anion of diphenylphosphinic acid acts as a monodentate ligand. Complexes 1-5 have been monitored for their solution stability using UV-vis spectroscopy. In the present study, cytotoxic activity of the complexes has been investigated on 2D human cell culture models (larynx carcinoma Hep2, hepatocellular carcinoma HepG2, breast carcinoma MCF-7 and nontumor lung fibroblasts MRC5) and 3D HepG2 human cell model. 1,10-Phenanthroline based complexes have demonstrated the highest cytotoxicity superior to the reference drug cisplatin. The level of reactive oxygen species generation in Hep2 cells has been shown to increase after incubation with complexes.

The [Re6Te8(imzH)6]2+ cationic cluster complex prepared by the interaction of [Re6Te8 (TeI2)6]I2·[Re6Te8(TeI2)4(TeI3)2]·I2 with imidazole (imzH) in a sealed glass ampoule at 200 °C for 48 h. The composition of the obtained compound is confirmed by 1H NMR spectroscopy and high-resolution mass spectrometry. The single crystals suitable for SC-XRD are prepared by slow diffusion of diethyl ether vapors into a solution of the complex in DMF. According to the SC-XRD data, the resulting complex has the composition [Re6Te8(imzH)6]I2·2/3DMF. The compound crystallizes in the monoclinic crystal system, P21/c space group, with the following unit cell parameters: a = 18.0379(4) Å, b = 17.9945(5) Å, c = 33.1318(7) Å, β = 115.1829(10)°, V = 9732.0(4) Å3, Z = 6. It is also shown that this compound exhibits solid-state luminescence with an emission maximum at 730 nm characteristic of octahedral rhenium cluster complexes.

Octahedral metal clusters [{M6X8}L6]2- (where M = Mo2+ or W2+, X = Cl-, Br- or I-, and L is an apical ligand typically with a charge of 1-) have shown promise in a great variety of applications, ranging from solar energy and catalysis to cancer diagnostics and therapy. However, these clusters are not stable in water - the most widely used medium in many practical fields. An effective way to utilize and stabilize these compounds is to incorporate them into organic matrices. Along with direct impregnation, clusters can be used as monomers in polymerization process due to the ease of an addition of polymerizable functional groups in cationic part or in apical ligand environment. In this work, new cluster with six terminal glycolate ligands, (Bu4N)2[{Mo6I8}(OOCCH2OH)6], has been obtained and studied using FTIR, TGA, EDX, etc. Cluster luminescence has been studied in the temperature range of 77-300 K. As have been demonstrated experimentally and theoretically, by the DFT calculations, the coordination of glycolic acid to the cluster drastically reduces the activity of the -OH group in the polymerization of polyurethane.

Coinage metal(i) complexes exhibiting thermally activated delayed fluorescence (TADF) have attracted worldwide attention as emitters for OLEDs. Reducing the emission lifetime and improving the quantum efficiency of such emitters is a current challenge in this hot field. To address this issue (challenge), a symmetry-based design strategy has been applied herein to obtain pseudo-symmetric complexes [M2(tdpb)(NHC)2]2+ (M = Cu, Ag, Au) scaffolded by 1,2,4,5-tetrakis(diphenylphosphino)benzene (tdpb) and N-heterocyclic carbene (NHC) ligands. In the solid state at ambient temperature, the synthesized compounds exhibit cyan to yellow TADF of the metal-to-ligand charge transfer type with excellent quantum yields (58-89%) and short decay times (2.5-15 mu s). It is shown that the symmetry-based design strategy leads to a significant increase in the radiative rate constants for the "dimers" [M2(tdpb)(NHC)2]2+ compared to the "monomers" [M(dppb)(NHC)]+ based on 1,2-bis(diphenylphosphino)benzene (dppb). The practical potential of the developed TADF emitters was also demonstrated through their application as innovative thermo- and vapor-chromic emission inks for advanced anti-counterfeiting labels.

Low‐cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high‐tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral‐at‐metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(–)‐menthol‐derived 1,10‐phenanthroline ligand (L*). These complexes exhibit a yellow CP‐TADF with a record‐high quantum yield (close to 100%) and high dissymmetry factor (|glum| ~ 1×10–2). Remarkably, the above compounds also show a negative thermal‐quenching (NTQ) of luminescence in the 300–77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP‐TADF OLEDs displaying mirror‐imaged CPL bands with high |gEL| factors of 1.5×10–2 and the maximum EQE of 6.15%. Equally important, using the (+)‐[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP‐TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low‐cost and robust CP‐TADF emitters.

Luminescent [HL]2[ZnX4] [X = Cl, Br] tetrahalozincate(II) compounds with triphenylphosphonium cation (HL = Ph3PH) were isolated using hydrohalic acids. This study reports the synthesis, crystal structures, and photophysical properties of novel tetrahalozincate(II) compounds. The [HL]2[ZnCl4] and [HL]2[ZnBr4] crystallize in the P21/c monoclinic and Pbca rhombic space groups, respectively. The compounds exhibit a strong ultraviolet (UV-B, lambda max approximate to 290 nm) fluorescence and blue-green and green phosphorescence in solid state, with a high quantum efficiency (up to 78 %). The luminescence mechanism was investigated, revealing that the UV-B and green emissions are ascribed to the {ZnX4}h-{Ph3PH}e exciton-phonon emission, and the blue-green emission arises from the transition within the organic moiety. The [HL]2[ZnCl4] compound shows an unexpected upconversion luminescence at 305 nm under 405 nm excitation, presumably caused by stepwise two-photon absorption accompanied by proton-coupled electron transfer. The up-conversion luminescence make this compounds a promising candidate for simple and cost-effective materials for visible-to-ultraviolet converter devices.

Due to the combination of useful physicochemical properties (luminescence, X-ray contrast, etc.), octahedral molybdenum halide cluster complexes [Mo6X8L6]n have been the subject of active investigation during the last decades. The most common methods for synthesizing new compounds with organic ligands involve the use of silver salts of organic acids or the substitution of terminal methylate ligands. However, these methods often necessitate the use of special conditions, such as an inert atmosphere, absolute solvents, and silver salts, which can be costly. In contrast, aqua-hydroxo complexes formed by hydrolysis of many complexes are considered final unreactive products, despite the tendency for them to form. This work proposes a simple and affordable method for the preparation of hexaaqua and hexahydroxo iodide clusters of molybdenum from [Mo6I14]2- in a single step. Furthermore, the possibility of using such compounds as starting complexes for the synthesis of clusters with organic ligands such as pyrazole is discussed. The paper presents synthetic approaches, detailed characterization both in solid and in solution, and a study of the reactivity and luminescence properties of the obtained compounds. Hexaaqua or hexahydroxo molybdenum iodide cluster complexes obtained in one step were shown to be accessible complexes for synthesis of clusters with pyrazole or pyrazolate ligands.

A new path to synthesize Re6Te8 cluster complexes with organic ligands is described. Two new telluride octahedral rhenium cluster complexes with N- and P-donor ligands were obtained by the reaction of [{Re6Te8}(TeI2)(6)]I-2[{Re6Te8}(TeI2)(4)(TeI3)(2)]I-2 with pyrazole or triphenylphosphine at 200 degrees C for 48 h. Under these conditions, substitution of all terminal telluroiodide ligands and formation of [{Re6Te8}L-6]I-2 (L = pyrazole or triphenylphosphine) were achieved. Both compounds were characterized by elemental analysis, IR- and NMR-spectroscopy, HR-ESI-MS, and solid-state luminescence measurements. Both obtained compounds exhibit luminescence typical for octahedral rhenium cluster complexes in the red and near-IR spectra. In addition, single crystal structural analysis was performed for the cluster complex with pyrazole.

New methylsulfate complex (Bu4N)2[Мо6I8(O3SOCH3)6] (I) is synthesized by the reaction of (Bu4N)2[Mo6I8(C≡C–C(O)OCH3)6] with dimethyl sulfate (CH3)2SO4. According to the XRD data, the molybdenum atoms are coordinated by the monodentate methylsulfate ligands. In a DMSO solution, the complex undergoes solvolysis accompanied by the complete substitution of the methylsulfate ligands by the solvent molecules. A powder sample of cluster I luminesces (phosphorescence) with the emission maximum at a wavelength of 620 nm (77 K). Increasing temperature to 300 K results in the shift of the emission maximum to 650 nm and a decrease in the integral intensity by 1.6 times.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Over recent years, Mn(II)‐organic materials showing circularly polarized luminescence (CPL) have attracted great interest because of their eco‐friendliness, cheapness, and room temperature phosphorescence. Using the helicity design strategy, herein, chiral Mn(II)‐organic helical polymers are constructed featuring long‐lived circularly polarized phosphorescence with exceptionally high glum and ΦPL magnitudes of 0.021% and 89%, respectively, while remaining ultrarobust toward humidity, temperature, and X‐rays. Equally important, it is disclosed for the first time that the magnetic field has a remarkably high negative effect on CPL for Mn(II) materials, suppressing the CPL signal by 4.2‐times at B⃗$\vec{B}$ = 1.6 T. Using the designed materials, UV‐pumped CPL light‐emitting diodes are fabricated, demonstrating enhanced optical selectivity under right‐ and left‐handed polarization conditions. On top of all this, the reported materials display bright triboluminescence and excellent X‐ray scintillation activity with a perfectly linear X‐ray dose rate response up to 174 µGyair s−1. Overall, these observations significantly contribute to the CPL phenomenon for multi‐spin compounds and promote the design of highly efficient and stable Mn(II)‐based CPL emitters.

Two new tetrabromidocuprate(II) complexes with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydro-benzimidazole (1) and 1-hydroxy-4methyl-2-(pyridin-2-yl)-5-phenylimidazole (2) were synthesized and their structure established from single-crystal X-ray data. Compounds crystallized in the monoclinic space groups P21/ n and P21/c, respectively, where tetrabromidocuprate anions formed magnetic chains as inferred from the dis-tances between the halide ions of different [CuBr4]2 � units. Magnetization measurements showed that both compounds behave as well-isolated uniform S = 1/2 antiferromagnetic chains described by the one-dimensional Heisenberg antiferromagnetic model with intra-chain exchange interaction 2 J = 23 K (1) and 2 J = 33 K (2) (the Hamiltonian H = 2J n-ary sumation S i theory investigations provided complementa r y results for 1 and 2. A calculation of exchange coupling constants gave values of 2 J = 24 K (1) and 2 J = 39 K (2), in good agreement with the experiment. The quantu m theor y of atoms in molecules and non-covalent interaction analyses showed that halogen bonding determined the ex-change interaction between [CuBr4] 2 � units in magnetic chains of these cation-anion compounds. Si+1). Electron paramagnetic resonance, optical absorption, and density functional