Synthesis and Characterization of Novel Cobalt Carbonyl Phosphorus and Arsenic Clusters.

Phosphorus- and arsenic-containing cobalt clusters are an interesting class of compounds that continue to provide new structures with captivating bonding patterns. Although the first members of this family were reported 45 years ago, the number of such species is still limited within the broad family of transition metal complexes bearing pnictogen atoms. Herein, we present the reaction of Co(CO) as a cobalt source with a number of phosphorus- and arsenic-containing compounds under variable reaction conditions.

Supramolecular compounds assembled from the heteroleptic tetrahedral complex [{CpMo(CO)}(μ,η-AsSb)] and metal salts.

The reaction of the tetrahedral complex [{CpMo(CO)}(μ,η-AsSb)] with Cu and Ag salts is presented which gives unprecedented neutral and cationic supramolecular aggregates featuring mixed As/Sb-donor molecules as ligands/linkers between metal ions.

Novel synthetic route towards heteroleptic pnictogen-rich organometallic-inorganic coordination compounds.

The reaction of the Ag(I) dimer [Ag(η-A)(μ,η:η-A)][TEF] (A = [{CpMo(CO)}(μ,η-P)]) possessing labile η-coordinated P ligands with the organometallic dipnictogen compounds [{CpMo(CO)}(μ,η-EE')] (E = E' = As, Sb; E = P, E' = As, Sb) represents a facile synthetic route towards unprecedented heteroleptic pnictogen-rich supramolecular complexes. This method can also be extended to the analogous Cu(I) dimer and is studied by DFT computations.

Organometallic-Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp Mo (CO) (μ,η -Sb )], Ag Ions and N-Donor Molecules as Building Blocks.

The reactions of the organometallic ligand complex [Cp Mo (CO) (μ,η -Sb )] (C) with Ag[TEF] ([TEF] =[Al{OC(CF ) } ] ) in the presence of a number of di- or polytopic N-donor molecules (1,6,7,12-tetraazaperylene (L1), 2,2'-bipyrimidine (L2), 4,4'-bipyridine (L3), trans-1,2-di(4-pyridyl)ethylene (L4) and 1,3-di(4-pyridyl)propane (L5)), were studied. Depending on the reaction stoichiometry and choice of linker, these reactions lead to the selective formation of dimeric or tetrameric supramolecular coordination complexes as well as 1D and 2D coordination polymers (CPs). The presented compounds are unique examples of supramolecular complexes incorporating both organometallic Sb-donor and organic N-donor molecules as ligands to stabilize metal ions.

Three- and Five-Membered Anionic Chains of Pnictogenylboranes.

An unprecedented family of three- and five-membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H E'-BH -NMe (E'=P, As) with pnictogen-based nucleophiles MER1R2 (E=P, As; R1=H, R2= Bu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18-crown-6)][H E'-BH -EH Bu] (3: E=E'=P; 4: E=E'=As; 5: E=As, E'=P) and [M(C)][H E'-BH -EPh ] (7: E=E'=P, M=Na, C=18-crown-6; 8: E=E'=As; M=K, C=[2.2.

Diantimony Complexes [Cp Mo (CO) (μ,η -Sb )] (Cp =C H , C H Bu) as Unexpected Ligands Stabilizing Silver(I) (n=1-4) Monomers, Dimers and Chains.

Synthesis and reactivity of transition metal compounds bearing "naked" pnictogen atoms is an active research area with remarkable bonding patterns observed in the formed compounds. Within this field, intense investigations on the coordination behavior of complexes possessing P and As (2≤n≤5) moieties have been conducted. However, studies on heavier analogues have been ignored so far due to arduous challenges related to low yields and moderate air stability.

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.

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.

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.

The Potential of the Diphosphorus Complex [CpW(CO)(η-P)] as an Organometallic Connecter in Supramolecular Chemistry.

For the first time, the tetrahedral diphosphorus complex [CpW(CO)(µ,η:η-P)] (Cp = CH) () is used as a connecter in supramolecular chemistry. The treatment of with Cu halides leads to the formation of the new one-dimensional (1D) linear polymers [Cu(µ-X){CpW(CO)(µ,η:η:η:η-P)}] {X = Cl (), Br (), I ()}. The coordination polymers (CPs) - are almost insoluble in organic solvents, thus, their P MAS-NMR spectra were recorded and found to be remarkably influenced by their solid-state structures.

The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry.

The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp Mo (CO) (μ,η :η -PE)] (Cp=C H ; E=As (1), Sb (2)), with Cu halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo PE units and the Cu halide, the oligomers [⟨{Cp Mo (CO) }{μ ,η :η :η :η -PE}⟩ ⟨{CuX}{Cu(μ-X)}⟩ ] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) or the 1D coordination polymers [{Cp Mo (CO) }{μ ,η :η :η :η -PAs}{Cu(μ-I)}] (5) and [{Cp Mo (CO) }{μ ,η :η :η :η -PSb} {Cu(μ-X)} ] (X=I (8), Br (9)) are accessible. These solid-state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo PE complexes 1 and 2 as linking moieties.

Highly soluble Cu(i)-acetonitrile salts as building blocks for novel phosphorus-rich organometallic-inorganic compounds.

The synthesis of the air-stable and highly soluble Cu(i)-acetonitrile salts [Cu(CH3CN)3.5][FAl] (1) ([FAl] = FAl{OC(C6F10)(C6F5)}3) and [Cu(CH3CN)4][TEF] (2) ([TEF] = Al{OC(CF3)3}4) is presented. Compound 1 reacts with the organometallic polyphosphorus complexes [Cp2Mo2(CO)4(η2-P2)] (A) and [(Cp*Fe(η5-P5)] (B) and salt 2 reacts with B to form one new (3) and three unprecedented (4-6) phosphorus-rich Cu(i) dimers with the general formulas [Cu2(μ,η1:η1-A)2(η2-A)2][FAl]2 (3), [Cu2(μ,η1:η1-A)2(η1-CH3CN)4][FAl]2 (4), [Cu2(μ,η1:η1-B)2(η1-CH3CN)4][FAl]2 (5) and [Cu2(μ,η1:η1-B)2(η1-CH3CN)4][TEF]2 (6).

Adaptive Coordination-Driven Supramolecular Syntheses toward New Polymetallic Cu(I) Luminescent Assemblies.

A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle A behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, a variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, a homometallic Cu(I) 1D-helical coordination polymer C and CuM discrete circular heterobimetallic assemblies D (M = Ni, Pd, Pt) are obtained. Their luminescence behaviors are studied, revealing notably the crucial impact of the spin-orbit coupling offered by the central M metal center on the photophysical properties of the heterobimetallic D derivatives.

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)] ().

Can Coordination-Driven Supramolecular Self-Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

The reaction between a preassembled Cu bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano-capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers.

Preorganized Ag Bimetallic Precursor with Labile Diphosphorus Ligands for a Programmed Synthesis of Organometallic-Organic Hybrid Polymers.

An Ag dimer capped with labile organometallic diphosphorus ligands [Cp Mo (CO) (η -P )] (Cp=C H ) acts as a highly pre-organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic-organic hybrid coordination polymers upon reaction with ditopic pyridine-based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

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.

The Diphosphorus Complex [CpMo(CO)(η-P)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers.

The three-component reaction of the tetrahedral diphosphorus complex [CpMo(CO)(η-P)] (), with Ag[BF] () in the presence of 2,2'-bipyrimidine () leads to the formation of the two novel two-dimensional networks and . Compound is a new two-dimensional organometallic-organic hybrid polymer, while derivative represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions.

Self-Assembly of Reactive Linear Cu3 Building Blocks for Supramolecular Coordination Chemistry and Their Reactivity toward E(n) Ligand Complexes.

This study describes the selective synthesis of linear, trinuclear, halide-bridged Cu(I) complexes [Cu3(μ-X)2(μ-dpmp)2(MeCN)2](+) (1a: X = Cl; 1b: X = Br; 1c: X = I) stabilized by the tridentate dpmp ligand obtained by self-assembly reactions in THF/MeCN. Upon drying, the MeCN ligands can be removed and the complexes are transformed to the reactive parent trinuclear [Cu3(μ-X)2(μ-dpmp)2](+) (2a-c) building blocks with two vacant coordination sites on the terminal Cu atoms. Another synthesis in CH2Cl2 directly yields 2a-c.

Organometallic polyphosphorus and -arsenic ligands as linkers between pre-assembled linear Cu(I) fragments.

A simple and straightforward synthesis of a new linear trinuclear Cu(I) cluster with polyphosphine ligands is presented. The reaction of this pre-organized Cu3 precursor with En ligand complexes (E = P, As; n = 2, 5) affords discrete complexes exhibiting end-on η(1)-coordination of the E2 ligands or one-dimensional coordination polymers featuring σ-1,3-bridging E5 rings, respectively.