Tetramerization of BEB-Doped Phenalenyls to Obtain (BE)-[16]Annulenes (E = N, O).

Two (BE)-[16]annulenes were prepared and fully characterized by experimental and quantum-chemical means (, E = N; , E = O). The 1,8-naphthalenediyl-bridged diborane(6) served as their common starting material, which was treated with [Al(NH)]Cl to form (91% yield) or with 1,8-naphthalenediboronic acid anhydride to form (93% yield). As a result, the heteroannulenes and are supported by four aromatic "clamps" and may also be viewed as NH- or O-bridged cyclic tetramers of BNB- or BOB-doped phenalenyls.

A lens-shaped supramolecule based on the bulky pentaphosphaferrocene [CpFe(η-P)] and CuBr.

Besides inherent fullerene-like hollow spheres, the metallasupramolecular chemistry of pentaphosphaferrocenes and CuBr afforded a conceptually new product, a compact 3.2 nm sized supramolecule [{1d}(CuBr)(CHCN)] formed by six largest pentaphosphaferrocene units [CpFe(η-P)] (1d: Cp = η-C(4-BuCH)) so far and a framework of 32 copper and 32 bromide ions.

Interplay of Anisotropic Exchange Interactions and Single-Ion Anisotropy in Single-Chain Magnets Built from Ru/Os Cyanidometallates(III) and Mn(III) Complex.

Two novel heterobimetallic compounds {[Mn(SB)M(CN)]·4HO} (SB = N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate) based on orbitally degenerate cyanidometallates [Os(CN)] () and [Ru(CN)] () and Mn Schiff base complex were synthesized and characterized structurally and magnetically. Their crystal structures consist of electrically neutral, well-isolated chains composed of alternating [M(CN)] anions and square planar [Mn(SB)] cations bridged by cyanide groups. These -ion magnetic anisotropy of Mn centers.

Across the Dimensions: A Three-Component Self-Assembly of Pentaphosphaferrocene-based Coordination Polymers.

Pentaphosphaferrocenes [Cp Fe(η -P )] (Cp*=η -C Me ) (A), Cp''=η -C H tBu -1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF . Adding rigid aromatic dinitriles ortho/meta/para-(NC) C H in a one-pot reaction between [Cp Fe(η -P )] and AgSbF leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC) C H play a key role in the formation of the isolated CPs.

Structural Chemistry of Giant Metal Based Supramolecules.

The review presents a bird-eye view on the state of research in the field of giant nonbiological discrete metal complexes and ions of nanometer size, which are structurally characterized by means of single-crystal X-ray diffraction, using the crystal structure as a common key feature. The discussion is focused on the main structural features of the metal clusters, the clusters containing compact metal oxide/hydroxide/chalcogenide core, ligand-based metal-organic cages, and supramolecules as well as on the aspects related to the packing of the molecules or ions in the crystal and the methodological aspects of the single-crystal neutron and X-ray diffraction of these compounds.

Unusual molecular complexes of antimony fluoride dimers with acetonitrile and pyridine: structures and bonding.

The structures of two new molecular complexes of antimony pentafluoride with pyridine (Py) and acetonitrile (AN), SbF·Py and SbF·AN, and a molecular complex of antimony trifluoride SbF·Py and its ionic derivative [HPy][SbF] in the solid state have been determined by single crystal X-ray structural analysis. The complexes SbF·AN and SbF·Py are the first structurally characterized compounds of dimeric antimony fluorides. To reveal the nature of bonding in the complexes and their stability, DFT computations of the electronic structure and thermodynamic characteristics were performed, in particular the analysis of the electrostatic potentials, the orbital interactions and the topology.

Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex.

By reacting [{Cp‴Fe(CO)}(µ,η-P)] () with in situ generated phosphenium ions [PhP][A] ([A] = [OTf] = [OSCF], [PF]), a mixture of two main products of the composition [{Cp‴Fe(CO)}(µ,η-P(CH))][PF] ( and ) could be identified by extensive P NMR spectroscopic studies at 193 K. Compound was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.

Use of a -P building block - a way to networks of host-guest assemblies.

Despite the proven ability to form supramolecular assemblies coordination to copper halides, organometallic building blocks based on four-membered -P ligands find only very rare application in supramolecular chemistry. To date, only three types of supramolecular aggregates were obtained based on the polyphosphorus end-deck complexes CpTa(CO)(η-P) (: Cp = Cp''; : Cp = Cp'''), with none of them, however, possessing a guest-accessible void. To achieve this target, the use of silver salts of the weakly coordinating anion SbF was investigated as to their self-assembly in the absence and in the presence of the template molecule PSe.

Versatile Coordination of Ag and Cu Ions towards cyclo-As Ligands.

The reactions of the cyclo-As complex [Cp*Fe(η -As )] (B) with the Ag and Cu salts of the weakly coordinating anion (WCA) [FAl{OC F (C F )} ] ([FAl] ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η  : η -B) ][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag cation between two π-coordinating cyclo-As ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo-As ligands in B.

Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes.

Whereas the self-assembly of pentaphosphaferrocenes [CpFe(η-P)] (Cp = Cp*, Cp, and Cp) with Cu and Ag salts has been well-studied in the past, the coordination chemistry toward Au complexes has been left untouched so far. Herein, the results of the self-assembly processes of [CpFe(η-P)] with Au salts of different anions (GaCl, SbF, and Al(OC(CF)) (TEF)) are reported. Next to a variety of molecular coordination products, the first coordination polymers based on polyphosphorus ligand complexes and Au salts are also obtained.

Three-Component Self-Assembly Changes its Course: A Leap from Simple Polymers to 3D Networks of Spherical Host-Guest Assemblies.

One-pot self-assembly reactions of the polyphosphorus complex [Cp*Fe(η -P )] (A), a coinage metal salt AgSbF , and flexible aliphatic dinitriles NC(CH ) CN (x=1-10) yield 1D, 2D, and 3D coordination polymers. The seven-membered backbone of the dinitrile was experimentally found as the borderline for the self-assembly system furnishing products of different kinds. At x<7, various rather simple polymers are exclusively formed possessing either 0D or 1D Ag/A structural motifs connected by dinitrile spacers, while at x≥7, the self-assembly switches to unprecedented extraordinary 3D networks of nano-sized host-guest assemblies (SbF )@[(A) Ag ] (x=7) or (A)@[(A) Ag ] (x=8-10) linked by dinitriles.

The Missing Parent Compound [(C H )Fe(η -P )]: Synthesis, Characterization, Coordination Behavior and Encapsulation.

The so far missing parent compound of the large family of pentaphosphaferrocenes [CpFe(η -P )] (1 b) was synthesized by the thermolysis of [CpFe(CO) ] with P using the very high-boiling solvent diisopropylbenzene. It was comprehensively characterized by, inter alia, NMR spectroscopy, single crystal X-ray structure analysis, cyclic voltammetry and DFT computations. Moreover, its coordination behavior towards Cu halides was explored, revealing the unprecedented 2D polymeric networks [{CpFe(η -P )}Cu (μ-X) ] (2 a: X=Cl, 2 b: X=Br) and [{CpFe(η -P )}Cu(μ-I)] (3) and even the first cyclo-P -containing 3D coordination polymer [{CpFe(η -P )}Cu(μ-I)] (4).

Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp Mo (CO) (μ,η -As )], Ag Salts and N-Donor Organic Molecules.

The reaction of the organometallic diarsene complex [Cp Mo (CO) (η -As )] (1) with Ag[Al{OC(CF ) } ] (Ag[TEF]) yielded the Ag monomer [Ag(η -1) ][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic-organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2'-bipyrimidine (L1) yielded the dicationic molecular compound [{(η -1) Ag} (μ-L1)][TEF] (3) or the 1D polymer [{(η -1)Ag}(μ-L1)] [TEF] (4) depending on the ratio of the reactants.

Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine.

Weakly or "partially" bonded molecules are an important link between the chemical and van der Waals interactions. Molecular structures of six new SbBr -Py complexes in the solid state have been determined by single-crystal X-ray diffraction analysis. In all complexes all Sb atoms adopt a pseudo-octahedral coordination geometry which is completed by additional Sb⋅⋅⋅Br contacts shorter than the sum of the van der Waals radii, with Br-Sb⋅⋅⋅Br angles close to 180°.

The Potential of the Diarsene Complex [(C H ) Mo (CO) (μ,η -As )] as a Connector Between Silver Ions.

The reaction of the organometallic diarsene complex [Cp Mo (CO) (μ,η -As )] (B) (Cp = C H ) with Ag[FAl{OC F (C F )} ] (Ag[FAl]) and Ag[Al{OC(CF ) } ] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η -B) Ag ][FAl] (4), [(μ,η :η -B) (η -B) Ag ][TEF] (5) and [(μ,η :η -B) Ag ][TEF] (6). These products are only composed of the complexes B and Ag . Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [Ag ] units stabilized by organometallic bichelating ligands.

Iodination of cyclo-E -Complexes (E=P, As).

In a high-yield one-pot synthesis, the reactions of [Cp*M(η -P )] (M=Fe (1), Ru (2)) with I resulted in the selective formation of [Cp*MP I ] salts (3, 4). The products comprise unprecedented all-cis tripodal triphosphino-cyclotriphosphine ligands. The iodination of [Cp*Fe(η -As )] (6) gave, in addition to [Fe(CH CN) ] salts of the rare [As I ] (in 7) and [As I ] (in 8) anions, the first di-cationic Fe-As triple decker complex [(Cp*Fe) (μ,η -As )][As I ] (9).

Metal-Deficient Supramolecule Based on a Fivefold-Symmetric Building Block.

An unprecedented cationic supramolecule [(Cp''Fe(η -P )) {CuNCMe} ] 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF ) } ] for the first time and characterized by X-ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal-deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal-deficient pentaphosphaferrocene-based supramolecules [{Cp Fe(η -P )} (CuX) ].

From nano-balls to nano-bowls.

Pentaphosphaferrocene [Cp*Fe(η-P)] in combination with Cu(i) halides is capable of a template-directed synthesis of fullerene-like spheres. Herein, we present the use of a triple decker complex as template that leads to the formation of unprecedented 'nano-bowls'. These spherical domes resemble the truncated fullerenes -C and represent a novel spherical arrangement in the chemistry of spherical molecules.

Organometallic-Organic Hybrid Polymers Assembled from Pentaphosphaferrocene, Bipyridyl Linkers, and Cu Ions.

A multicomponent approach of the P ligand complex [Cp*Fe(η-P)] (: Cp* = η-CMe) with the ditopic organic linkers 4,4'-bipyridine () or -1,2-di(pyridine-4-yl)ethene () in the presence of Cu salts of the anions [BF] and [PF] or the coordinating anion Br, leads to the formation of four novel organometallic-organic hybrid polymers: the cationic 1D polymeric compounds [Cu{Cp*Fe(µ,η-P)}(µ,η-CHN)(CHCN)] [BF] () and [Cu{Cp*Fe(µ,η-P)}(µ,η-CHN)(CHCN)] [PF] () as well as the unique neutral threefold 2D → 2D interpenetrated networks [CuCl{Cp*Fe(µ,η-P)}(µ,η-CHN)] () and [CuBr{Cp*Fe(µ,η-P)}(µ,η-CHN)] ().

Neutral two-dimensional organometallic-organic hybrid polymers based on pentaphosphaferrocene, bipyridyl linkers and CuCl.

The reaction of the P ligand complex [Cp*Fe(η-P)] (1: Cp* = η-CMe) with CuCl in the presence of 4,4'-bipyridine or 1,2-di(4-pyridyl)ethylene leads to the formation of three unprecedented neutral 2D organometallic-organic hybrid networks, the constitutional isomers [CuCl{Cp*Fe(μ,η-P)}(μ,η-CHN)] (2 and 3) and the coordination polymer [(CuCl){Cp*Fe(μ,η-P)}(μ,η-CHN)] (4) with isomeric square (2 and 3) and honeycomb (4) layer topologies.

Anionic Hosts for the Incorporation of Cationic Guests.

Pentaphosphaferrocene [Cp*Fe(η -P )] (1 a) represents an excellent building block for the template-directed synthesis of spherical supramolecules. Here, the self-assembly of 1 a with Cu and Cu halides in the presence of the template complexes [FeCp ][PF ], [CoCp ][PF ] and [CoCp ] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp ] is enclosed in unprecedented anionic organometallic hosts.

Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [CpMo(CO)(η-P)] Complex and Silver(I) Salts.

The reactions of the tetrahedral diphosphorus [CpMo(CO)(η-P)] (; Cp = CH) complex with Ag[Al{OC(CF)}] (AgTEF) () and Ag[FAl{OC(CF)(CF)}] (AgFAl) () were studied. The first reaction led to the formation of the [Ag(η-)(η:η-)][TEF] () dimer and the [Ag(η:η-)] [TEF] () coordination polymer, whereas the second reaction afforded the [Ag(η:η-)(η-CHCl)(η-CH)][FAl] () or the [Ag(η-)(η:η-)][FAl] () dimer and the [Ag(η:η-)] [FAl] () coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure.

Transfer Reagent for Bonding Isomers of Iron Complexes.

The cothermolysis of As and [Cp″Zr(CO)] (Cp″ = η-CHtBu) results in the formation of [Cp″Zr(η-As)] (1) in high yields and the arsenic-rich complex [(Cp″Zr)(Cp″Zr)(μ,η-As)] (2) as a minor product. In contrast to yellow arsenic, 1 is a light-stable, weighable and storable arsenic source for subsequent reactions. The transfer reaction of 1 with [Cp‴Fe(μ-Br)] (Cp‴ = η-CHtBu) yields the unprecedented bond isomeric complexes [(Cp‴Fe)(μ,η-As)] (3a) and [(Cp‴Fe)(μ,η-cyclo-As)] (3b).

An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers.

Pentaphosphaferrocenes [Cp Fe(η -P )] (1) and Cu halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF SO ) for the construction of the novel 2D polymer [{Cp*Fe(μ ,η -P )}{Cu(CF SO )}] (2) and the unprecedented nanosphere (CH Cl ) @[{Cp Fe(η -P )} {Cu(CF SO )} ] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron.

Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments.

The redox chemistry of [Cp*Fe(η -As )] (1, Cp*=η -C Me ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η -P )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme) ][{Cp*Fe(μ,η -As )} ] (2) and the arsenic-rich complexes [K(dme) ] [(Cp*Fe) (μ,η -As )] (3), [K(dme) ] [(Cp*Fe) (μ,η -As )] (4), and [K(dme) ] [(Cp*Fe) (μ ,η -As )] (5).