Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H₃L and H₅L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu₄(HL²⁻)₂(N₃)₄]·4CH₃OH·56H₂O (1) and [Cu₄(L³⁻)₂(OH)₂(H₂O)₂] (2), dinuclear [Cu₂(H₃L1²⁻)(N₃)(H₂O)(NO₃)] (3), polynuclear {[Cu₂(H₃L1²⁻)(H₂O)(BF₄)(N₃)]·H₂O}_n (4), heptanuclear [Cu₇(H₃L1²⁻)₂(O)₂(C₆H₅CO₂)₆]·6CH₃OH·44H₂O (5), and decanuclear [Cu₁₀(H₃L1²⁻)₄(O)₂(OH)₂(C₆H₅CO₂)₄] (C₆H₅CO₂)₂·20H₂O (6). X-ray studies have revealed that the basic building block in 1, 3, and 4 is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL²⁻ or H₃L1²⁻, and one μ-1,1-azido (N₃⁻) ion and in 2, 5, and 6 by μ-phenoxide oxygen of L³⁻ or H₃L1²⁻ and μ-O²⁻ or μ₃-O²⁻ ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (1 and 6), 2D-sheets (3), and 3D-structures (4). In 5, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In 1, 3, and 5, Cu(II) ions in [Cu₂] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm⁻¹.     

Syntheses and X-ray structures of complexes with (η-allyl)Mo-units in oxygen-rich coordination spheres

The reaction of Mo(η³-C₃H₄(CH₃))(CH₃CN)₂(CO)₂Cl with AgBF₄ in THF yields the cationic complex [Mo(η³-C₃H₄(CH₃))(CH₃CN)₂(CO)₂(THF)]⁺[BF₄]⁻, 1, whose X-ray structure has been determined. Oxo nucleophiles are capable of replacing the weakly bound THF molecule in 1 and under simultaneous loss of CH₃CN the resulting complexes aggregate to oligonuclear compounds. Accordingly, the reactions with NaOMe and KOH yield [Na(THF)₄]⁺[(η³-C₃H₄(CH₃))(CO)₂Mo(μ-OCH₃)₃Mo(CO)₂(η³-C₃H₄(CH₃))]⁻, 2 and [K(18-crown-6)]⁺[[Mo(η³-C₃H₄(CH₃))(CO)₂]₃(μ₂-OH)₃(μ₃-OH)]⁻, 3, which were characterized by means of single crystal X-ray diffraction. Due to fluoride abstraction from BF₄⁻ the reaction of 1 with KOH also yields fluorinated derivatives of 3 but incorporation of fluorine in 3 can be avoided if AgO₃SCF₃ rather than AgBF₄ is used to generate the cation of 1. For purposes of comparison the dinuclear complex [K(18-crown-6)]⁺[[Mo(η³-C₃H₄(CH₃))(CO)₂]₂(μ₂-F)₃]⁻, 4, has been prepared, too, showing fluoride bridges and KF bonding. The chemical properties and the structures of these compounds in solution as well as their role as structural models for intermediates during molybdenum oxide catalysed propene oxidation are discussed.     

Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid

Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the π electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)–Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)₂·2H₂O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(μ-Pip)₂(4-Acpy)]₂ (1); a mixture of one dimer and two monomers [Zn(µ-Pip)(Pip)(Isn)₂]₂·2[Zn(Pip)₂(HPip)(Isn)]·2MeOH (2); and two dimers [Cd(μ-Pip)(Pip)(4-Acpy)₂]₂ (3) and [Cd(μ-Pip)(Pip)(Isn)₂]₂·MeOH (4). They exhibit bridged (1, µ₂-η¹:η¹), bridged, chelated and monodentated (2, µ₂-η¹:η¹, µ₁-η¹:η¹ and µ₁-η¹), or simultaneously bridged and chelated (3 and 4, µ₂-η²:η¹) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations.     

Synthesis,Characterization and Crystal Structures of New Ruthenium Carbonyl Clusters Derived from (9-Anthracenyl)diphenylphosphine*

Thermal reaction of [Ru₂(CO)₆(μ-PFu₂)(μ-η¹,η²-Fu)] (Fu=2-furyl) with (9-anthracenyl)diphenylphosphine (AnPPh₂) produces a novel diruthenium complex [Ru₂(CO)₅(μ-PFu₂)(μ-η¹,η¹,η²-C₁₄H₈PPh₂)] (1) in good yield whereas the corresponding reaction between [(μ-H)₄Ru₄(CO)₁₂] and AnPPh₂ gives [HRu(CO)₃(PPh₂C₁₄H₈)][(μ-H)₄Ru₄(CO)₁₁(AnPPh₂)] (2). Both compounds 1 and 2 were fully characterized by spectroscopic methods and their X-ray crystal structures were determined. For 1, initial coordination of the PPh₂ functionality at the Ru atom is accompanied by cyclometalation of the anthracenyl ring to form a Ru–C σ bond together with concomitant formation of a π bond to the adjacent Ru center and loss of the furyl ligand. The formation of 2 involves the cleavage of two Ru–Ru bonds, and the making of a Ru–P bond, followed by orthometalation of the anthracenyl ring. The optical absorption and emission spectra of 1 were recorded and the results were correlated to the DFT calculations.Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday.     

Synthesis,bonding properties and ether activation reactivity of cyclobutadienyl-ligated hybrid uranocenes

A series of hybrid uranocenes consisting of uranium(iv) sandwiched between cyclobutadienyl (Cb) and cyclo-octatetraenyl (COT) ligands has been synthesized, structurally characterized and studied computationally. The dimetallic species [(η⁴-Cb′′′′)(η⁸-COT)U(μ:η²:η⁸-COT)U(THF)(η⁴-Cb′′′′)] (1) forms concomitantly with, and can be separated from, monometallic [(η⁴-Cb′′′′)U(THF)(η⁸-COT)] (2) (Cb′′′′ = 1,2,3,4-tetrakis(trimethylsilyl)cyclobutadienyl, COT = cyclo-octatetraenyl). In toluene solution at room temperature, 1 dissociates into 2 and the unsolvated uranocene [(η⁴-Cb′′′′)U(η⁸-COT)] (3). By applying a high vacuum, both 1 and 2 can be converted directly into 3. Using bulky silyl substituents on the COT ligand allowed isolation of base-free [(η⁴-Cb′′′′)U{η⁸-1,4-(ⁱPr₃Si)₂C₈H₆}] (4), with compounds 3 and 4 being new members of the bis(annulene) family of actinocenes and the first to contain a cyclobutadienyl ligand. Computational studies show that the bonding in the hybrid uranocenes 3 and 4 has non-negligible covalency. New insight into actinocene bonding is provided by the complementary interactions of the different ligands with uranium, whereby the 6d orbitals interact most strongly with the cyclobutadienyl ligand and the 5f orbitals do so with the COT ligands. The redox-neutral activation of diethyl ether by [(η⁴-Cb′′′′)U(η⁸-C₈H₈)] is also described and represents a uranium-cyclobutadienyl cooperative process, potentially forming the basis of further small-molecule activation chemistry.

The synthesis, structure and bonding in a series of hybrid uranocenes consisting of cyclobutadienyl and cyclo-octatetraenyl ligands is described.     

From a nanoparticular solid-state material to molecular organo-f-element-polyarsenides

A convenient pathway to new molecular organo-lanthanide-polyarsenides in general and to a f-element complex with the largest polyarsenide ligand in detail is reported. For this purpose, the activation of the solid state material As⁰_nano (nanoscale gray arsenic) by the multi electron reducing agents [K(18-crown-6)][(Ln^+II)₂(μ-η⁶:η⁶-C₆H₆)] (Ln = La, Ce, Cp′′ = 1,3-bis(trimethylsilyl)cyclopentadienyl anion) and [K(18-crown-6)]₂[(Ln^+II)₂(μ-η⁶:η⁶-C₆H₆)] (Ln = Ce, Nd) is shown. These non-classical divalent lanthanide compounds were used as three and four electron reducing agents where the product formation can be directed by variation of the applied reactant. The obtained Zintl anions As₃³⁻, As₇³⁻, and As₁₄⁴⁻ were previously not accessible in molecular 4f-element chemistry. Additionally, the corresponding compounds with As₁₄⁴⁻-moieties represent the largest organo-lanthanide-polyarsenides known to date.

Reaction of non-classical divalent lanthanide compounds with nanoparticulate gray arsenic via three- and four-electron reduction led to a series of new f-element polyarsenides, including the largest f-element polyarsenide known to date.     

The reactions of [Co(η-C5H5)(CO)(L)] (L = R3P or RNC) with carbon disuphide and organoisothiocyanates

The reactions of [Co(η-C₅H₅)(CO)(PR₃)] or [Co(η-C₅GH₅)(CO)₂]/R₃P mixtures (R = alkyl or aryl) with CS₂ in refluxing CS₂ or CS₂/toluene gives rise to [Co(η-C₅H₅)(PR₃)(CS)], [Co(η-C₅H₅)(PR₃)(CS₂)], [Co(η-C₅H₅)(PR₃)(CS₃)], and [Co₃(η-C₅H₅)₃ (CS)(S)] in reasonable yields. The corresponding reactions using PhNCS give [Co(η-C₅H₅)(PPh₃)(PhNCS)] and a polymeric species which appears to be [Co₄(η-C₅H₅)₄ (PhNCS)]. Similar products are obtained with [Co(η-C₅H₅)(CO)(CNR)] or [Co(η0C₅H₅)(CO)₂]/RNC mixtures.     

Mononuclear Transition Metal Cymantrenecarboxylates as Precursors for Spinel-Type Manganites

Novel mononuclear cymantrenecarboxylate complexes of transition metals, [Co(H₂O)₆](CymCO₂)₂·4H₂O (Cym = (η⁵-C₅H₄)Mn(CO)₃) (1), [Ni(H₂O)₆](CymCO₂)₂·4H₂O (2), [Zn(H₂O)₆](CymCO₂)₂·4H₂O (3), [Co(CymCO₂)₂(imz)₂] (imz = imidazole, 4), [Co(CymCO₂)₂(bpy)₂]·2PhMe (bpy = 2,2′-bipyridyl, 5), [Ni(CymCO₂)(bpy)₂(H₂O)][CymCO₂]·0.5MePh·2H₂O (6), [Cu(CymCO₂)₂(imz)₂] (7), and [Cu(CymCO₂)₂(bpy)(H₂O)] (8), were obtained and characterized by single-crystal X-ray analysis. Complexes 1–3 are isostructural. Magnetism of the Co complexes 1, 4, and 5 was studied; it was shown that they exhibit the properties of field-induced single-molecule magnets with magnetization reversal barriers (ΔE/k_B) of 44, 13, and 10 K, respectively. Thermal decomposition of complexes 1–8 was studied by means of DSC and TGA methods. The final products of thermolysis of 1–6 in air, according to powder XRD data, are the pure spinel phases MMn₂O₄; for the cases of copper complexes, the mixtures of CuMn₂O₄ and CuO were found in the products.     

η-Alkynyl and vinylidene transition metal complexes: 10. Reaction of the metal-acetylide [(η-C5H5)(CO)(NO)W---CC---C(CH3)3]Li with 1,2-diiodoethane as electrophile and with various nucleophiles

Treatment of the η¹-acetylide complex [(η⁵-C₅H₅)(CO)(NO)W---CC---C(CH₃)₃]Li (4) with 1,2-diiodoethane in THF at −78 °C, followed by the addition of Li---CC---R [R=C(CH₃)₃, C₆H₅, Si(CH₃)₃, 6a–6c] or n-C₄H₉Li and protonation with H₂O, afforded the corresponding oxametallacyclopentadienyl complexes (η⁵-C₅H₅)W(I)(NO)[η²-O=C(CC---R)CH=CC(CH₃)₃] (7a–7c), 8c and (η⁵-C₅H₅)W(I)(NO)[η²-O=C(n-C₄H₉)CH=CC(CH₃)₃] (9). The formation of these metallafuran derivatives is rationalized by the electrophilic attack of 1,2-diiodoethane onto the metal center of 4 to form first the neutral complex [(η⁵-C₅H₅)(I)(CO)(NO)W---CC---C(CH₃)₃] (5). Subsequent nucleophilic addition of Li---CC---R 6a–6c or n-C₄H₉Li and a reductive elimination step followed by protonation leads to the products 7a–7c and 9. One reaction intermediate could be trapped with CF₃SO₃CH₃ and characterized by a crystal structure analysis. The identity of another intermediate was established by infrared spectroscopic data. The oxametallacyclopentadienyl complex 10 forms in the presence of excess 1,2-diiodoethane through an alternative pathway and crystallizes as a clathrate containing iodine.     

Bis(diphenylphosphino)methane trimethylphosphine alkyl and η-cyclopentadienyl compounds of rhodium(I); P{H} two dimensional δ/J resolved and Overhauser effect nuclear magnetic resonance spectroscopy

Neutral mononuclear tertiary phosphine rhodium(I) complexes of the formula RhX(PMe₃)(dppm), X = Cl, CH₂SiMe₃, CH₂CMe₃, CH₂CMe₂Ph, η⁵-C₅H₅, DPPM = bis(diphenylphosphino)methane, RhCl(PPh₃)(dppm), RhX(dppm)₂, X = Cl, Me and Rh(η⁵-C₅H₅(dppm) have been synthesised. In Rh(η⁵-C₅H₅)(PMe₃)(dppm), the dppm ligand is unidentate according to ³¹P{¹H} NMR and X-ray data.The ³¹P{¹H} NMR spectral parameters of RhX(PR₃)(dppm) have been determined by a combination of two dimensional δ/J resolved spectroscopy and heteronuclear nuclear Overhauser effect difference spectroscopy (NOEDS) in conjunction with iterative analysis of the one dimensional spectra.     

Reactions of the cycloheptatrienyl complexes [MX(CO)2(η-C7H7)] (M=Mo, X=Br; M=W, X=I) with CNBu: X-ray crystal structure of [WI(CO)2(CNBu)2(η-C7H7)]

Reaction of [MX(CO)₂(η⁷-C₇H₇)] (M=Mo, X=Br; M=W, X=I) with two equivalents of CNBu^t in toluene affords the trihapto-bonded cycloheptatrienyl complexes [MX(CO)₂(CNBu^t)₂(η³-C₇H₇)] (1, M=Mo, X=Br; 2, M=W, X=I). The X-ray crystal structure of 2 reveals a pseudo-octahedral molecular geometry with an asymmetric ligand arrangement at tungsten in which one CNBu^t is located trans to the η³-C₇H₇ ring. Treatment of 2 with tetracyanoethene results in 1,4-cycloaddition at the η³-C₇H₇ ring to give [WI(CO)₂(CNBu^t)₂{η³-C₉H₇(CN)₄}], 3. The principal reaction type of the molybdenum complex 1 is loss of carbonyl and bromide ligands to afford substituted products [MoBr(CNBu^t)₂(η⁷-C₇H₇)] 4 or [Mo(CO)(CNBu^t)₂(η⁷-C₇H₇)]Br. Reaction of [MoBr(CO)₂(η⁷-C₇H₇)] with one equivalent of CNBu^t in toluene at 60°C affords [MoBr(CO)(CNBu^t)(η⁷-C₇H₇)], 5, which is a precursor to [Mo(CO)(CNBu^t)(NCMe)(η⁷-C₇H₇)][BF₄], 6, by reaction with Ag[BF₄] in acetonitrile. In contrast with the parent dicarbonyl systems [MoX(CO)₂(η⁷-C₇H₇)], complexes of the Mo(CO)(CNBu^t)(η⁷-C₇H₇) auxiliary, 5 and 6, do not afford observable η³-C₇H₇ products by ligand addition at the molybdenum centre.     

Synthesis and molecular structure of cisoid and transoid isomers of [Re2(CO)6(1,1′-bis(indenylidene)] derived from the reaction of [Re2(CO)8(MeCN)2] and diazoindene

The compound [Re₂(CO)₈(MeCN)₂] reacts with diazoindene (C₉H₆N₂) while refluxing in THF to afford three dirhenium products in which C₉H₆N₂ is cleaved with loss of N₂ and with incorporation of the residual indenylidene group into the products. Two indenylidene groups are coupled in two diastereomers of [Re₂(CO)₆(μ,η⁵:η⁵-1,1′-C₁₈H₁₂)] where C₁₈H₁₂=bis(indenylidene). X-ray structures show that these isomers are related as RR/SS and RS isomers. These have the two Re(CO)₃ groups coordinated transoid and cisoid, respectively to a trans bis(indenylidene) bridge. The third product is the μ-indenylidene complex [Re₂(CO)₈(μ,η¹:η⁵-C₉H₆)], which was also structurally characterised by X-ray diffraction.     

Cyclopentadienyl-ruthenium and -osmium chemistry : XXXIX. Syntheses of novel alkynyl-ruthenium complexes. X-Ray structures of two forms of {Ru(PPh3)2(η-C5H5)}2(μ-C4) and of Ru{CCC(O)Me}(PPh3)2(η-C5H5)

Reactions between [Ru(thf)(PPh₃)₂(η-C₅H₅)]⁺ and lithium acetylides have given further examples of substituted ethynylruthenium complexes that are useful precursors of allenylidene and cumulenylidene derivatives. From Li₂C₄, mono- and bi-nuclear ruthenium complexes were obtained: single-crystal X-ray studies have characterised two rotamers of {Ru(PPh₃)₂(η-C₅H₅)}₂(μ-C₄), which differ in the relative cis and trans orientations of the RuL_n groups. Protonation of Ru(CCCCH)(PPh₃)₂(η-C₅H₅) afforded the butatrienylidene cation [Ru(C=C=C=CH₂)(PPh₃)₂(η-C₅H₅)]⁺, which reacted readily with atmospheric moisture to give the acetylethynyl complex Ru{CCC(O)Me}(PPh₃)₂(η-C₅H₅), also fully characterised by an X-ray structural study.     

Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(μ-L1Clpz)]_n (L1Clpz⁻ = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(μ-L1Clpz)]₃}₂ with (ⁿBu₄N)[Ag(CN)₂]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(μ-L1Clpz)]₃}₂. The Ag···Ag distances in [Ag(μ-L1Clpz)]_n are slightly shorter than twice Bondi’s van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag–N distances in [Ag(μ-L1Clpz)]_n were found: 2.0760(13) and 2.0716(13) Å, and their N–Ag–N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(μ-L1Clpz)]_n in the solid-state are different from those of {[Ag(μ-L1Clpz)]₃}₂ (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.     

Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids

The functionalization of the arsenic transfer reagent [Cp″₂Zr(η^1:1-As₄)] (1) focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of 1 towards different Lewis-acidic transition metal complexes and main group compounds is investigated by experimental and computational studies. Depending on the steric requirements of the Lewis acids and the reaction temperature, a variety of new complexes with different coordination modes and coordination numbers could be synthesized. Depending on the Lewis acid (LA) used, a mono-substitution in [Cp″₂Zr(µ,η^1:1:1:1-As₄)(LA)] (LA = Fe(CO)₄ (4); B(C₆F₅)₃ (7)) and [Cp″₂Zr(µ,η^3:1:1-As₄)(Fe(CO)₃)] (5) or a di-substitution [Cp″₂Zr(µ₃,η^1:1:1:1-As₄)(LA)₂] (LA = W(CO)₅ (2); CpMn(CO)₂ (3); AlR₃ (6, R = Me, Et, ⁱBu)) are monitored. In contrast to other coordination products, 5 shows an η³ coordination in which the butterfly As₄ ligand is rearranged to a cyclo-As₄ ligand. The reported complexes are rationalized in terms of inverse coordination.     

Preparation of closo-10-vertex transition metal carbaboranes

The synthesis of the ten-vertex closo-metallacarboranes 10-η₅H₅Ni-η⁴-1-CB₈H₉, 6-η⁵-C₅H₅Ni-η⁵-1-CB₈H₉, (η⁵-C⁵Ni)₂-1-CB₇H₈, and [2-η⁵-C₅H₅Co-η⁵-1-CB₈H₉]⁻ from 4-CB₈H₁₄ is reported.     

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs,and other topologies

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with Cu^I and/or Cu^II cations that show a remarkable range of framework topologies and structures. Complex [Cu^I ₄Cu^II _1.5(L1)₃(CN)₆]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu₃(L2)₄(H₂O)₃]·6(OTf)·n(DMSO) 2 and [Cu₂(L3)₂Br₂(H₂O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4³.12³)(4².12²) topology or a coordination chain. Complex [Cu₂(L1)₂(OTf)₂(NMP)₂(H₂O)₂]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6².8)(6².8)(4.6².8²) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF₄·2(CH₃CN)·H₂O 5 features a 2D network of 6³ topology while the Cu^II analogue [Cu₂(L1)₂(NMP)(H₂O)]·4BF₄·12NMP·1.5H₂O 6 has an interpenetrating (10,3)-b type structure and complex [Cu₂(L2)₂Br₃(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.8² topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C₆₀ through soaking the crystals in a toluene solution.     

Cyclodextrin Rotaxanes of Pt Complexes and Their Conversion to Pt Nanoparticles

The cationic Pt complex (Pt(NC₆H₄-C₆H₄N-(CH₂)₁₀-O(C₆H₃-3,5-(OMe)₂)(MeN-(CH₂CH₂NMe₂)₂))⁺ was prepared by the reaction of alkylbipyridinium ligand with a nitrateplatinum(II) complex. Mixing the complex and α- and β-cyclodextrins in aqueous media produced the corresponding [2]rotaxanes with 1:1 stoichiometry. γ-Cyclodextrin and the Pt complex formed a rotaxane having components in a 1:1 or 2:1 molar ratio. The results of mass and nuclear magnetic resonance (NMR) measurements confirmed the rotaxane structures of the Pt complexes. Transmission electron microscopy (TEM) and atomic force microscope (AFM) analyses revealed the formation of micelles or vesicles. The addition of NaBH₄ to the rotaxanes in aqueous media formed Pt nanoparticles with diameters of 1.3–2.8 nm, as characterized by TEM. The aggregated size of the nanoparticles formed from the rotaxane did not change even at 70 °C, and they showed higher thermal stability than those obtained from the reduction of the cyclodextrin-free Pt complex.     

A novel cis-push–pull effect in cycloruthenated azobenzene thiocarbonyl-containing complexes: crystal and molecular structures of [RuX(CS)(η-C,N-C6H4N=NPh)(PPh3)2](X=Cl, I)

Treatment of [RuHCl(CS)(PPh₃)₃] with Hg(o-C₆H₄N=NC₆H₅)₂ affords [RuCl(CS)(η²C,N-o-C₆H₄N=NC₆H₅)(PPh₃)₂] (1) in good yield, where the cyclometallated azobenzene ligand coordinates through an ortho-C and one azo-N to give a five-membered chelate ring. Reaction of 1 with AgNO₃ followed by NaBr or NaI affords the chloride-exchanged products [RuX(CO)(η²C,N-o-C₆H₄N=NC₆H₅)(PPh₃)₂] (2, 3), whereas reaction of 1 with AgOC(O)Me or NaS₂CNEt₂·2H₂O gives the halide mono-phosphine-substituted complexes [Ru(CS)(LL)(η²C,N-o-C₆H₄NNC₆H₅)(PPh₃)] (4, 5). In the solid-state structures of 1 and 3 there are significant changes in the bond lengths for the cyclometallated azobenzene ligand are observed relative to free azobenzene. These are discussed, with the aid of spectroscopic and crystallographic data, in terms of a cis-push–pull effect.     

Polymerisations of -caprolactone and β-butyrolactone with Zn-, Al- and Mg-based organometallic complexes

The reaction of EtAlCl₂ with 1,2-{LiN(PMes₂)}₂C₆H₄ (Mes = 2,4,6-Me₃C₆H₂) and of butyloctylmagnesium with 1,2-{NH(PPh₂)}₂C₆H₄ gave [AlEt(1,2-{N(PMes₂)}₂C₆H₄-κ²N,N′)(THF)] (1) and [Mg(1,2-{N(PPh₂)}₂C₆H₄-κ²N,N′)(THF)₂] (2), respectively. Complexes 1 and 2 were fully characterised by NMR (¹H, ¹³C, ³¹P) and IR spectroscopy and mass spectrometry. Complexes 1 and 2 were employed as catalysts in the polymerisation of -caprolactone, which produced polymers with a narrow molecular weight distribution. For comparison the polymerisations of -caprolactone and β-butyrolactone were carried out with the Zn complex [ZnPr{1-N(PMes₂)-2-N(PHMes₂)C₆H₄-κ²N,N′}] (3) as catalyst, which produced polymers with narrow molecular weight distributions and high molecular weights.