Band 69, Heft 8

The new lead strontium germanate PbSrGeO 4 was synthesized by a high-temperature solid-state reaction of lead(II) oxide, strontium carbonate, and germanium(IV) oxide at a temperature of 900 °C in a platinum crucible. The compound crystallizes in the orthorhombic space group P2 1 2 1 2 1 (no. 19) being isotypic to the structure of BaNdGaO 4 [1]. The primitive cell contains four formula units with lattice parameters of a = 995:40(2), b = 732:44(2), c = 599:42(2) pm, V = 437:02(2)Å 3 , and residuals of R 1 = 0:0385 and wR 2 = 0:0997 for all data. The main structural element of PbSrGeO 4 is an isolated [GeO 4 ] 4- tetrahedron. A circular arrangement of six of these [GeO 4 ] 4- tetrahedra leads to the formation of large channels along b in which the strontium cations are eightfold coordinated by oxygen atoms. The lead cations are coordinated by three oxygen atoms, and with a lone pair of electrons they show a pseudo-tetrahedral coordination. Next to the structural investigations, PbSrGeO 4 was characterized by Raman-spectroscopic investigations and DFT calculations. Graphical Abstract Synthesis and Characterization of the New Lead Strontium Germanate PbSrGeO 4

Orange TlCu 3 Er 2 S 5 crystallizes in the orthorhombic space group Cmcm (a = 391:27(2), b = 1382:91(7), c = 1630:54(8) pm, Z = 4). Its crystal structure contains one Tl + , one Er 3+ , two Cu + , and three S 2- ions as crystallographically unique components. All Cu + cations are coordinated by four S 2- anions to form [CuS 4 ] 7- tetrahedra, which have vertex- and edge-connectivity to build up 2 ∞ {[Cu 3 S 5 ] 7- } layers parallel to the (010) plane. The Er 3+ cations are octahedrally surrounded by six S 2- anions. These [ErS 6 ] 9 - units share trans-oriented edges forming linear chains, which are further linked by common vertices yielding 1 ∞ {[Er 2 S 10 ] 14- } double strands. Further fusion via common vertices results in 2 ∞ {[Er 2 S 5 ] 4- } layers parallel to the (010) plane. Alternatingly stacked along [010] and condensed via S 2- anions, these two types of layers form a three-dimensional framework, leaving tunnels along [100], where the Tl + cations fit in. These are each coordinated by eight S 2- anions in the shape of bicapped trigonal prisms. Tl 2 Cu 5 Er 3 S 8 was obtained as black single crystals with metallic luster (monoclinic, Cm, a = 1381:69(7), b = 390:73(2), c = 1435:98(7) pm, β = 111:132(3)°, Z =2). Four of the five crystallographically different Cu + cations are tetrahedrally surrounded by S 2- anions, whereas (Cu 3 ) + is situated in sulfur triangles. Connected via common vertices and edges, the copper-sulfur polyhedra form strongly corrugated 2 ∞ {[Cu 5 S 8 ] 11- } layers parallel to the (201) plane. All Er 3+ cations are again coordinated by six S 2- anions in the shape of [ErS 6 ] 9- octahedra. Their condensation via edges and vertices leads to 2 ∞ {[Er 3 S 8 ] 7- } layers spreading out parallel to the (010) plane. Both types of anionic layers result in a three-dimensional framework through sulfide fusion, which leaves tunnels running along [010] occupied by Tl + cations. The two crystallographically different Tl + cations both have eight coordinating S 2- anions forming bicapped trigonal prisms. Remarkably enough, the ion closest to (Tl1) + is not a S 2- anion (shortest Tl + -S 2- bond: 305 pm), but a (Cu 3 ) + cation at a distance of just 291 pm. Graphical Abstract A Structural Comparison of Two Thallium Copper Erbium Sulfides: TlCu 3 Er 2 S 5 and Tl 2 Cu 5 Er 3 S 8

A new coordination polymer [Zn(BDC-I 2 )(DMF)] n (1) has been prepared by solvothermal reaction of Zn(II) nitrate with 2,5-diiodo-1,4-benzenedicarboxylic acid (H 2 BDC-I 2 ) in ethanol-DMF, and characterized by elemental analysis, IR spectroscopy and single-crystal and powder X-ray diffraction techniques. Complex 1 shows a two-dimensional network possessing dinuclear Zn 2 (CO 2 ) 4 secondary building units, which are further assembled into a three-dimensional supramolecular structure through intermolecular C-H···I interactions. Solid-state properties such as photoluminescence and thermal stability of 1 have also been investigated. Graphical Abstract A New 2D Zinc(II)-Organic Framework with Dinuclear Units Based on Iodinated Terephthalate: Synthesis, Crystal Structure and Luminescence Behavior

A neutral metal-organic framework [CoNa 3 (1,2,3-Hbtb)(1,2,3-btb)] (1) has been synthesized through an ionothermal method using 1-ethyl-3-methylimidazolium bromide as solvent (1,2,3- H 3 btb=1,2,3-benzenetricarboxylic acid). The complex has been characterized by IR spectroscopy, elemental analysis, PXRD and single-crystal X-ray diffraction. The structure of 1 exhibits a layer network structure in which Co(II) is five-coordinated forming a distorted trigonal bipyramid. Na1 and Na3 are surrounded by seven oxygen atoms, and Na2 is six-coordinated. In the structure, the anions of 1,2,3-H 3 btb are embedded in two bridging μ 8 coordination modes. The luminescence properties of 1 have been investigated in the solid state at room temperature. Graphical Abstract Ionothermal Synthesis and Crystal Structure of a Neutral 2D Metal- Organic Framework Based on Cobalt(II) 1,2,3-Benzenetricarboxylate

A new Wells-Dawson-based organic-inorganic honeycomb hybrid compound, namely [Cd 3 (H 2 biim) 6 P 2 W 18 O 62 ]·2H 2 O (1) (H 2 biim=2,2´-biimidazole), was hydrothermally synthesized by using a cadmium salt, the biimidazole ligand and the Wells-Dawson-type POM, and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. In compound 1, each polyoxoanion cluster [P 2 W 18 O 62 ] 6- is coordinated by six [Cd(H 2 biim) 2 ] 2+ subunits via six of its terminal oxygen atoms on two equatorial sites. Each [Cd(H 2 biim) 2 ] 2+ subunit links two adjacent polyoxoanions. Thus, the linking styles of the [P 2 W 18 O 62 ] 6- and [Cd(H 2 biim) 2 ] 2+ subunits induce a honeycomb-like layer. The electrochemical and photocatalytic properties of the title compound have been studied. Graphical Abstract A New Wells-Dawson-based Organic-Inorganic Honeycomb Hybrid Compound with Cadmium Bis(2,2´-biimidazole) Spacers

Reactions of a flexible fluorinated ligand, 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-ylmethyl) benzene (Fbix), with ZnX 2 (X =OAc- or NO 3 - ) lead to the formation of the two new Zn II coordination polymers [Zn(Fbix)(OAc) 2 ] n (1) and {[Zn 2 (Fbix) 3 (NO 3 ) 2 ](NO 3 ) 2 (H 2 O) 3 } n (2), which have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Although the Zn II centers of both 1 and 2 are in a similar tetrahedral coordination geometry, each Zn II ion in 1 is surrounded by two Fbix spacers and two terminal OAc - anions to form a highly undulated chain, whereas each Zn II ion in 2 is embraced by three Fbix ligands and one NO 3 - anion to result in a two-dimensional cationic network. Since 1 and 2 are synthesized under the same conditions, the structural differences between them are attributable to the difference of the counterions. The solid-state properties such as thermal stability and luminescence of 1 and 2 have also been studied briefly. Graphical Abstract Anion Effect on the Structural Diversity of 1-D and 2-D Zinc(II) Coordination Polymers with a Flexible Fluorinated Bis(imidazole) Ligand

Raspberry and ginger ketones have been synthesized in good yield by the hydrogenation of the corresponding unsaturated precursors 4-(4´-hydroxyphenyl)but-3-en-2-one and 4-(4´-hydroxy-3´- methoxyphenyl)but-3-en-2-one, respectively, using a freshly prepared suspension of nickel boride in methanol as catalyst. Graphical Abstract Synthesis of Raspberry and Ginger Ketones by Nickel Boride-catalyzed Hydrogenation of 4-Arylbut-3-en-2-ones

Porphyrins with exocyclic rings allow for significant modulation of the photochemical properties of the macrocycle via modulation of the aromatic system through electronic and conformational effects. Here we sought to generate such porphyrinoids via a stepwise strategy involving two cycloaddition steps, the first improving the synthesis of a relatively unstable dehydropurpurin intermediate which ring opens to form a key 1,5-diketone species. A library of a new class of porphyrinoids, namely diazepine-fused porphyrinoids was synthesized via condensation methods from these 1,5-diketone precursors in yields of 8 - 49%. Cycloaddition methodologies were also applied to bisporphyrins, and their reactivities were investigated Graphical Abstract Synthesis of Diazepine-fused Porphyrinoids and Annulated Porphyrin Arrays

This paper presents a method for introducing toluene and bromobenzene moieties into 1,2,4- triazines as an alternative to cross-coupling reactions. It is demonstrated that the C=N bond of a wide range of 1,2,4-triazines undergoes addition of arenes in the presence of AlCl 3 . Graphical Abstract Arylation of 1,2,4-Triazines in the Presence of AlCl 3

The P,N-substituted ferrocene [Fe{η 5 -C 5 H 4 -P(S)Ph 2 }(η 5 -C 5 H 4 -NHCH 2 tBu)] was prepared in six steps from the bromo derivative [Fe{η 5 -C 5 H 4 -PPh 2 }(η 5 -C 5 H 4 -Br)]. Its reductive desulfurisation with Raney nickel afforded the corresponding phosphino-substituted derivative [Fe(η 5 -C 5 H 4 - PPh 2 )(η 5 -C 5 H 4 -NHCH 2 tBu)]. Both compounds have been structurally characterised by singlecrystal X-ray diffraction studies. Graphical Abstract Synthesis and Crystal Structures of the P,N-Substituted Ferrocenes [Fe{η 5 -C 5 H 4 –P(S)Ph 2 }(η 5 -C 5 H 4 –NHCH 2 tBu)] and [Fe(η 5 -C 5 H 4 – PPh 2 )(η 5 -C 5 H 4 –NHCH 2 tBu)]

A new series of 2-amino-6-((4-aryldiazenyl)benzyloxy)-4-chloropyrimidine derivatives 4 - 13 and 2,6-diamino-5-arylazo-4-chloro-pyrimidine analogs 15 - 20 were synthesized from the pyrimidine scaffolds 3 and 14, respectively, via diazotization with various amines. Nucleophilic displacement at the 2,4-diamino-5-arylazo-6-chloro-pyrimidine 16 by different amines afforded the 4-alkylamino analogs 21 - 27. All new compounds were evaluated for their in vitro anti-HIV activity in MT-4 cells as non-nucleoside reverse transcriptase inhibitors on the basis of our previous work. Screening results indicated that 10 and 11 were found to be the only compounds in the series inhibiting HIV-1 replication in cell cultures with EC 50 of >1:23 and >2:92 μg mL -1 of a CC 50 of 12.30 and 17.52 μg mL -1 , resulting in a selectivity index of 10 and 6, respectively. In addition, preliminary structure-activity relationships and molecular modeling of these new analogs are detailed in this manuscript. Graphical Abstract Synthesis and Modeling Study of Some Potential Pyrimidine Derivatives as HIV Inhibitors

The formal [3+3] cyclization of 1,3-bis(silyloxy)-1,3-butadienes with 2-aryldiazenyl-3-silyloxy- 2-en-1-ones afforded a variety of functionalized diaryl-diazenes. Graphical Abstract Synthesis of Functionalized Diaryldiazenes by Formal [3+3] Cyclizations of 1,3-Bis(silyloxy)-1,3-butadienes with 2-Aryldiazenyl-3-silyloxy-2-en-1- ones