An unexpected sulfinate–sulfonate mixed coordination polymer of copper(II)

By reaction of copper nitrate trihydrate and 2,2′-dipyridyldisulfide in both aerobic and anaerobic conditions, the mixed [{Cu(2-pySO₂)₂}_n]–[{Cu(2-pySO₃)₂}_n] coordination polymer of copper(II) (1) has been synthesized. The X-ray diffraction analysis indicates that complex 1 exhibits an infinite one-dimensional polymeric chain consisting of [Cu(C₅H₄N)₂] building units connected by SO₂/SO₃ groups. The atom which has been labelled O3 is only present in 60% of the molecules. Complex 1 exhibits a very weak ferrogmagnetic spin coupling (zJ = +0.40 cm⁻¹).     

Synthesis, characterization and crystal structure of cis,mer-[ReH(CO)2{PPh(OMe)2}3]

The dicarbonylhydride complex cis,mer-[ReH(CO)₂{PPh(OMe)₂}₃] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)₂ in [ReH(CO)₃(L)] (L = PPh₂OCH₂CH₂OPPh₂), this complex was treated with PPh(OMe)₂ under UV irradiation. The complex 1 was characterized by IR, ¹H and ³¹P{¹H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration showed by the X-ray crystallographic analysis of the complex. The environment of the metal centre is a distorted octahedron.     

Solvothermal in situ formation of a hexanuclear copper(I) complex with 2-thiolate-N,N′-dimethylnicotinamide

Solvothermal reaction of 2-mercaptonicotinic acid (HL¹) with copper(II) nitrate in DMF/methanol medium leads to the production of a novel hexanuclear complex [Cu(L²)]₆ · (H₂O)₂ (1), in which in situ formation of an anionic ligand 2-thiolate-N,N′-dimethylnicotinamide (L²) and reduction of copper(II) to copper(I) are observed. X-ray single-crystal structure of 1 reveals that each copper(I) center adopts a trigonal geometry provided by two thiolate and one pyridyl groups from three separated L² ligands. As a result, six copper(I) ions are interconnected by six μ₃–L² bridges to afford a hexanuclear cluster, in which the octahedral Cu₆ core is stabilized by significant cuprophilic interactions.     

Double O,C,O-chelated diorganotin(IV) cation

The synthesis of double O,C,O-chelated diorganotin(IV) compound L₂SnBr₂ (1), where L is 2,6-(MeOCH₂)₂C₆H₃^?, the precursor for the synthesis of Sn ← O intramolecularly coordinated organotin(IV) cations is reported. Treatment of compound 1 with SnBr₄ yielded the double O,C,O-chelated diorganotin(IV) ionic pair [L₂SnBr]⁺ [SnBr₅·THF]^? (2). Both compounds 1 and 2 were characterized by ¹H, ¹³C, ¹¹⁹Sn NMR and molecular structure of compound 2 was established by X-ray diffraction.     

Controllable assembly of a 3-D metal–organic supramolecular framework with the inclusion of a well-resolved 1-D water morph

Two mixed-ligand metal–organic complexes [Cd₂(adipato)(phen)₂(NO₃)₂(H₂O)₂](H₂O)₆ (1) and {[Cd(adipato)(phen)](H₂O)₃}_n (2) have been synthesized upon the reaction of Cd(II) nitrate with 1,10-phenanthroline (phen) and adipate under similar conditions. For 1, the adipato-bridged dinuclear entities are extended into a 3-D supramolecular architecture via hydrogen bonds and π–π stacking. Interestingly, a well-resolved 1-D water morphology consisting of alternate cyclic water tetramer and hexamer is detected as the guests in each channel of this 3-D lattice. Whereas 2 represents a layered coordination polymer in which the Cd^II centers are interlinked by adipate dianions via different coordination modes.     

Self-assembled chloro-bridged metallo-prismatic cations of the general formula [M6(η-C5Me5)6(μ3-tpt)2(μ-Cl)6] (M = Rh, Ir; tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine)

Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(η⁵- C₅Me₅)(μ-Cl)Cl]₂ (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (1) and [Ir₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (2), respectively. Addition of silver triflate to 1 and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (3) and [Ir₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by ¹H NMR, IR and UV/visible spectroscopy.     

Synthesis and structural characterization of new one-dimensional rhodium complexes

New one-dimensional Rh^I–Rh^II complexes [Rh₂(OOCMe)₂(phen)₂]_n(PF₆)_n·0.5nMe₂CHOH, 1 and [Rh₂(OOCMe)₂(bpy)₂]_n(PF₆)_n·nH₂O, 2 have been synthesized and characterized. The compound 1 is molecular wire with the shortest Rh(I)–Rh(II) distances, anions and solvate molecules occupy channels between parallel cationic wires.     

Self-assembly of a 1D helical manganese coordination polymer and a tetranuclear lanthanum complex with 1,10-phenanthroline and 3,5-dinitrosalicylato dianion

The hydrothermal reaction of manganese chloride and lanthanum nitrate with 3,5-dinitrosalicylic acid (3,5-(NO₂)₂sal) and 1,10-phenanthroline (phen) yielded two compounds [Mn(phen){3,5-(NO₂)₂sal²⁻}]_n (1) and La₂(phen)₃{3,5-(NO₂)₂sal²⁻}₂ (NO₃)(OH) (2). Magnetic susceptibility measurements show weak antiferromagnetic interactions in (1).     

Unusual iron-mediated C–N bond formation and synthesis of the Fe(III) complex of a polypyridine ligand with one carboxamide group

A high-spin iron(III) chloro complex [(PaPPy₃)Fe(Cl)](ClO₄) (1, where =N,N-bis(2-pyridylmethyl)amine-N-propyl-2-pyridine-2-carboxamide) has been synthesized via the “template effect” and structurally characterized. The template reaction leads to the formation of a new carbon–nitrogen bond from coupling of a primary alkyl chloride with a secondary amine.     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Photoinduced linkage isomerism of binuclear bis(pyrazole-3,5-dicarboxylato)-bridged {RuNO} centres

The two novel binuclear pyrazole-3,5-dicarboxylato-bridged {RuNO}⁶ complexes K₂[{Ru(NO)Cl}₂(μ-pzdc)₂] (1) and [{Ru(NO)(H₂O)}₂(μ-pzdc)₂]·4H₂O (2) (pzdc = pyrazole-3,5-dicarboxylate) were synthesized and characterized by elemental analysis, mass spectrometry and spectroscopic methods (NMR, UV–vis, IR). 2 was investigated by means of single-crystal X-ray diffraction analysis. On irradiation, in both 1 and 2 the existence of photoinduced long-lived metastable isonitrosyl states SI were detected by low-temperature infrared spectroscopy.     

Synthesis, crystal structure and photophysical properties of a series of new neutral iridium(III) complexes with 2-phenylpyridine

A series of new neutral iridium(III) complexes containing strong-field ancillary ligands, [Ir(ppy)₂(PPh₃)L] (ppy = 2-phenylpyridine, PPh₃ = triphenylphosphine, L = NCS⁻, 1; , 2; NCO⁻, 3), have been synthesized and fully characterized by ¹H NMR, IR, ESI mass spectral and elemental analysis. The crystal structure of 1 has been determined by X-ray analysis. The photoluminescence (PL) spectra of 1–3 show emission maxima at 477, 489 and 485 nm, respectively, corresponding to blue light-emitting of 1 and blue-green light-emitting of 2 and 3. PL quantum yields (PLQYs) of 1–3 are 0.39, 0.13 and 0.43, respectively.     

Rhodium(I) iminophosphine poly(propyleneimine) dendrimers: Synthesis, characterization and molecular structure of a mononuclear analogue

First (G1)- and second-generation (G2) poly(propyleneimine) (PPI) dendrimers were reacted with 2-(diphenylphosphino)benzaldehyde, to form iminophosphine-functionalised dendritic ligands (1, 2). The reaction of the dimeric precursor [RhCl(CO)₂]₂ with the heterobidentate dendritic ligands 1, 2 gave the corresponding rhodium(I) complexes (3, 4).     

Ionothermal synthesis of a new cobalt metal-organic framework based on tetranuclear cobalt clusters

A new metal-organic network (EMIM)[Co₂(hip)₂(μ₃-OH)]·H₂O (1), (H₂hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been synthesized by the ionothermal reaction of cobalt nitrate, H₂hip and [EMIM]Br ionic liquid. Single-crystal X-ray diffraction analysis reveals that 1 exhibits a two-dimensional (2D) bilayer constructed from tetranuclear [Co₄(μ₃-OH)₂] building units and hip²⁻ linkers. There are square cavities with the dimension of 10.161 × 10.868 Å. The [EMIM]⁺ cations are located in the cavities, which have the hydrogen bonding interactions with the bilayer. Further more, the strong hydrogen bonds between the carboxylate and hydroxyl oxygen atoms of hip²⁻ ligands and lattice water molecules extend the 2D layer into a 3D supramolecular network. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that there exist antiferromagnetic interactions.     

Metallosupramolecular isomerism: Switching from a cyclic to a chain assembly induced by benzo-fusion within a bridging ligand

Reaction of silver nitrate with 1,4-bis(2-quinolyloxy)benzene (4) gave a one-dimensional coordination polymer (5) in which there is extensive π–π stacking of the quinoline units.     

Structure and photocatalytic property of a new Cu(II) based framework with jsm topology

A new coordination polymer [Cu(mip)(bpy)_0.5]_n (1) was obtained through reaction of 5-methylisophthalic acid (H₂mip) and 4,4′-bipyridine (bpy) with copper nitrate under hydrothermal condition. X-ray single crystal diffraction analysis reveals that complex 1 exhibits a 3D network with jsm topology. Photocatalytic activity of the complex has also been characterized. Notably, complex 1 represents the rare example of visible-light-driven photocatalyst based on coordination polymer and shows good degradation ability over methylene blue (MB).     

Synthesis,solid-state and in-solution structures of a new seven coordinated manganese(II) complex via X-ray diffraction and electrospray ionization mass spectrometry

The structure of the [Mn(HPClNOL)(η₁-NO₃)(η₂-NO₃)] 1 complex [HPClNOL = 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol] in the solid-state and in H₂O/MeOH solution was investigated by monocrystal X-ray diffraction and ESI(+)–MS/MS. X-ray reveals that 1 is a seven-coordinated complex with a discrete mononuclear structure in which the manganese(II) ion is coordinated by the tripodal HPClNOL ligand and two nitrate ions, one monodentate and the other bidentate. ESI(+)–MS/MS shows that mononuclear, dinuclear and trinuclear manganese cationic species are present in solution, probably in equilibrium with neutral 1. This contrasting scenario illustrates for 1 the importance of both solid-state and in-solution characterizations of coordination compounds with potential bioinorganic interest.     

Efficient ring-opening polymerization of -caprolactone using anilido-imine–aluminum complexes in the presence of benzyl alcohol

A number of new anilido-imine–Al complexes ortho-C₆H₄(CHNAr¹)(NAr²)AlMe₂ [Ar¹ = C₆H₅, Ar² = C₆H₅ (2a); Ar¹ = 2,6-Me₂C₆H₃, Ar² = 2,6-Me₂C₆H₃ (2b); Ar¹ = 2,6-Et₂C₆H₃, Ar² = 2,6-Et₂C₆H₃ (2c); Ar¹ = 2,6-ⁱPr₂C₆H₃, Ar² = 2,6-Me₂C₆H₃ (2d); Ar¹ = 2,6-ⁱPr₂C₆H₃, Ar² = 2,6-Et₂C₆H₃ (2e)] were synthesized, characterized and used as initiators for the ring-opening polymerization of -caprolactone in the presence of benzyl alcohol. The effect of initiator structure and reaction conditions, such as benzyl alcohol/Al molar ratio and reaction temperature on the reactivity, and polymer molecular weight were investigated. The polymerization of -caprolactone initiated by these complexes was found to take place in an immortal fashion.     

Synthesis, crystal structures and photoluminescence properties of Sm-based enantiomeric pair

Novel Sm-based enantiomeric pair, generally formulated Sm(DBM)₃L (L_R,R in 1, L_S,S in 2, DBM = dibenzoylmethanate) have been successfully prepared via the reaction of Sm(DBM)₃·2H₂O with chiral ligands L_R,R (−)-4,5-pinene bipyridine and L_S,S (+)-4,5-pinene bipyridine (Scheme 1), respectively. The crystal structure analysis of 1 and 2 reveal that they crystallize in chiral space group P2₁ of monoclinic system. The central Sm(III) ion is octacoordinate with six β-diketonate oxygen atoms and two chiral pinene bipyridine nitrogen atoms, forming a coordination polyhedron best described as the distorted square antiprism (SA). The CD spectra (Fig. S1) further confirm that 1 and 2 are enantiomers. The photoluminescence investigations of 1 and 2 demonstrate that they display deep-red luminescence characteristic of the Sm³⁺_.     

Two uranyl–organic frameworks with pyridinecarboxylate ligands. A novel heterometallic uranyl–copper(II) complex with a cation–cation interaction

Reaction of uranyl nitrate with pyridine-2-carboxylic acid (HL¹) under hydrothermal conditions gives the complex [(UO₂)₃(L¹)₄(NO₃)₂], 1, which differs from the previously reported molecular complex, obtained at room temperature, by the absence of water, coordinated and free, and the extended carboxylate bridging. Although the trimetallic basic unit is similar in both cases, 1 crystallizes as a two-dimensional assembly. A heterometallic complex results from the reaction of uranyl nitrate and copper(II) trifluoromethanesulfonate with nicotinic acid (pyridine-3-carboxylic acid, HL²), [UO₂Cu(L²)₂(NO₃)₂], 2, in which copper nicotinate two-dimensional subunits are bridged by uranyl nitrate groups to give a three-dimensional framework. The copper atom environment geometry is elongated octahedral, with one of the axial donors being a uranyl oxo group (cation–cation interaction).