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[BMIm][Sn(AlCl4)3] (1) ([BMIm]: 1-butyl-3-methylimidazolium), [BMPyr][Sn(AlCl4)3] (2) ([BMPyr]: 1-butyl-1-methyl-pyrrolidinium), and [BMIm][Pb(AlCl4)3] (3) are obtained by reaction of SnCl2/PbCl2 in [BMIm]Cl/[BMPyr]Cl/AlCl3-based ionic liquids. The colourless crystals of the title compounds contain infinite 1∞[M(AlCl4)3]n- chains (M: Sn, Pb) that are separated by the voluminous [BMIm]+/[BMPyr]+ cations. The central Sn2+/Pb2+ is coordinated by chlorine in the form of distorted squared anti-prismatic polyhedra. Each Cl atom, in turn, is part of an [AlCl4]- tetrahedron that interlinks Sn2+/Pb2+ to the chain-like building unit. In addition to the novel structural arrangement, all title compounds surprisingly show intense white-light emission. Although Sn2+ and Pb2+ are well-known as dopants in conventional phosphors, efficient luminescence via s-p-transitions of compounds containing Sn2+/Pb2+ in molar quantities and as regular lattice constituents is rare. The emission of [BMIm][Sn(AlCl4)3] and [BMPyr][Sn(AlCl4)3] is very efficient with quantum yields of 51 and 76%, which belong to the highest values known for s-p-based luminescence of Sn2+.

The novel tellurium rhenium carbonyls [TeI2Re(CO)5][AlCl4] (1), [BMIm][Te2I4(μ-I)2Re(CO)4] (2), {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) and [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) were prepared by reacting TeI4 and Re2(CO)10 in ionic liquids (ILs). [TeI2Re(CO)5][AlCl4] (1) was obtained in a mixture of [BMIm]Cl (BMIm: 1-butyl-3-methylimidazolium) and AlCl3 (ratio: 1 : 1) and contains a [TeI2Re(CO)5]+ cation. Increasing the amount of AlCl3 ([BMIm]Cl : AlCl3 = 1 : 2) results in [BMIm][Te2I4(μ-I)2Re(CO)4] (2) with the anion [Te2I4(μ-I)2Re(CO)4]-. At a [BMIm]Cl to AlCl3 ratio of 1 : 3, {Te3I2(μ-I)3(μ3-I)}Re(CO)3 (3) was realized with a Te3I3 ring and μ3-coordinating iodine. Finally, [BMIm][(Te2)3{Re(CO)3}2{Re(CO)4}3] (4) was prepared in [BMIm][OTf] (OTf: triflate) and contains the ufosan-like anion [(Te2)3{Re(CO)3}2{Re(CO)4}3]- with three Te22- and two Re(CO)3+ units that establish a distorted heterocuban-like cage. The compounds were characterized by single-crystal structure analysis, energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), and infrared spectroscopy (FT-IR). The course of the reaction and the formation of the four novel tellurium-rhenium carbonyls can be directly correlated to the reaction conditions and especially to the acidity of the IL.

[Pb{Mn(CO)5}3][AlCl4] containing a trigonal planar PbMn3 cluster was obtained by the reaction of PbCl2 and Mn2(CO)10 in the ionic liquid [BMIm][AlCl4]. The title compound is composed of [Pb{Mn(CO)5}3]+ carbonyl cations and [AlCl4]- anions that are connected to infinite zig-zag chains. The [Pb{Mn(CO)5}3]+ cation exhibits a central PbMn3 cluster with three equal Pb-Mn single bonds, resulting in an almost equilateral triangle of three manganese atoms with a formal Pb+I in its center. Such a cluster and compound were identified for the first time. In addition to single-crystal structure analysis, the composition, structure and properties were further characterized by density functional theory (DFT) calculations, energy dispersive X-ray spectroscopy (EDXS), and Fourier-transform infrared spectroscopy (FT-IR), as well as optical spectroscopy (UV-Vis).

Correction for 'Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr 4 ][IBr 2 ] and [PBr 4 ][I 5 Br 7 ]' by David Hausmann et al., Dalton Trans., 2016, 45, 16526-16532.

The phosphorus interhalides [PBr 4 ][IBr 2 ] (1) and [PBr 4 ] 2 [I 5 Br 7 ] (2) were prepared by reaction of PBr 5 and the interhalogen IBr in the ionic liquid [MeBu 3 N][N(Tf) 2 ] (N(Tf) 2 : bis(trifluoromethylsulfonyl)amide). [PBr 4 ][IBr 2 ] (1) consists of tetrahedral [PBr 4 ] + cations and linear [IBr 2 ] - anions. [PBr 4 ] 2 [I 5 Br 7 ] (2) also contains [PBr 4 ] + cations as well as the iodine bromide anion [I 5 Br 7 ] 2- . The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br 2 ) of 96.8 wt% below 300 °C. For the ternary system P-Br-I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy.

Functionalized 4,4'-biphenyldicarboxylic acid molecules with additional amine, alkyne, azide or nitro groups were prepared and applied in the synthesis of novel metal-organic frameworks and mixed-linker metal-organic frameworks isoreticular to DUT-5. The properties of the frameworks could be tuned by varying the number of functional groups in the materials and the amine groups were employed in post-synthetic modification reactions without changing the framework structure or significantly decreasing the porosity of the materials.

The bimetallic metal-organic framework Cu-Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu(2+) by Ru(3+) centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy.

By reacting Fe(CO)(5) and SnI(4) in the ionic liquids [XIm][NTf(2)] (XIm: 1-ethyl-3-methylimidazolium/EMIm, 1-ethyl-imidazolium/EHIm, 1-propyl-3-methylimidazolium/PMIm; NTf(2): bistrifluoridomethansulfonimide), the compounds [XIm][FeI(CO)(3)(SnI(3))(2)] are obtained as transparent, dark red crystals. According to single-crystal structure analysis, the title compounds crystallize monoclinically and contain the anionic carbonyl complex [FeI(CO)(3)(SnI(3))(2)](-) as well as [EMIm](+), [EHIm](+) or [PMIm](+) cations. The anionic carbonyl is composed of a Sn-Fe-Sn barbell-shaped building unit with Fe-Sn distances of 252.0(1) pm. Herein, tin is coordinated distorted tetrahedrally by iodine; iron is coordinated pseudo-octahedrally by three carbonyl ligands, one iodine atom and two tin atoms. Bonding situation and valence state are investigated in detail for [EMIm][FeI(CO)(3)(SnI(3))(2)] based on bond-lengths considerations, infrared spectroscopy, Mössbauer spectroscopy, density functional theory and DFT-based Mulliken population analysis. Hence, the formal oxidation state of the metal atoms can be concluded to Fe(±0) and Sn(3+).

Dark red transparent crystals of [Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)][SnI{Co(CO)(4)}(3)](2) are obtained by reacting SnI(4), Co(2)(CO)(8) and 1,4-C(6)H(4)(CN)(2) in the ionic liquid [EMIm][NTf(2)] (EMIm: 1-ethyl-3-methylimidazolium; NTf(2): bis(trifluoromethylsulfonyl)imide). According to X-ray structure analysis based on single crystals, the title compound crystallizes in a triclinic manner and contains the novel (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] coordination network. This infinite 2D network is composed of Co(2+) ions that are planarily interlinked by four 1,4-dicyanobenzene ligands. As a non-charged 2D network, Co(2+) is furthermore coordinated by two [NTf(2)](-) anions. The (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] layers are stacked on top of each other with SnI[Co(CO)(4)](3) molecules intercalated in distorted cubic gaps between the layers. The title compound is furthermore characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), infrared spectroscopy (FT-IR) and optical spectroscopy (UV-Vis).