Correction: Multiple correlations between spin crossover and fluorescence in a dinuclear compound.

Correction for 'Multiple correlations between spin crossover and fluorescence in a dinuclear compound' by Chun-Feng Wang et al., Chem. Commun., 2016, 52, 14322-14325, https://doi.org/10.1039/C6CC07810A.

Multiple correlations between spin crossover and fluorescence in a dinuclear compound.

Multiple correlations between spin crossover and fluorescence are established in a dinuclear compound with fluorescence from d(Fe) + π(SCN) to π*(ligand) charge transfer and correlation originated from ligand to Fe(ii) energy transfer.

Dimeric 1,3-propanediaminetetraacetato lanthanides as the precursors of catalysts for the oxidative coupling of methane.

From neutral solutions, dimeric 1,3-propanediaminetetraacetato lanthanides (NH4)2[Ln2(1,3-pdta)2(H2O)4]·8H2O [Ln = La, 1; Ce, 2] and K2[Ln2(1,3-pdta)2(H2O)4]·11H2O [Ln = La, 3; Ce, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid, C11H18N2O8) were isolated in high yields. The reaction of excess strontium nitrate with 1 resulted in the formation of a two dimensional coordination polymer [La2(1,3-pdta)2(H2O)4]n·[Sr2(H2O)6]n·[La2(1,3-pdta)2(H2O)2]n·18nH2O (5) at 70 °C. Complexes 1-4 show a similar central molecular structure. The lanthanide ions are coordinated by two nitrogen atoms, four carboxy oxygen atoms from one 1,3-pdta ligand, two from the neighboring 1,3-pdta ligand forming a four-membered ring and two water molecules. Complex 5 has two kinds of dimeric lanthanum unit and extends into a 2D coordination polymer through strontium ions and bridged oxygen atoms, and forms a fourteen membered ring linked by oxygen atoms from carboxy groups of pdta. Complexes 1-4 are soluble in water. The (13)C{(1)H} NMR experiments for complex 1 were tested in solution. Thermal products from 1 and 5 show good catalytic activities towards the oxidative coupling reaction of methane (OCM). The conversion of methane and selectivity to C2 reached 29.7% and 51.7% at 750 °C for the product of 5. From TGA, XRD and SEM analyses, the thermal products from 1 and 5 are rod- and poly-shaped, which are assigned as lanthanum oxocarbonate and a mixture of La2O3, SrCO3 and La2O2CO3 for 1 and 5, respectively. The precursor method is favorable for the formation of regular shaped mixed oxides.

A lanthanum chelate possessing an open-channel framework with water nanotubes: properties and desalination.

A new type of thermally stable chelate {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 12nH2O (1) [1,3-H4pdtaCH2[CH2N(CH2CO2H)2]2] with an open-channel shows significant and unusual solvent transport properties and demonstrates a use for low-pressure desalination, which is constructed by cheap and available lanthanum salt and 1,3-propanediaminetetraacetate. The chelate could be converted reversibly to its trihydrate {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 3nH2O (1a), dehydrated product {La(H2O)4[La(1,3-pdta)(H2O)]3}n (1b) and ethanol adduct {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 3nH2O · 3nEtOH (1c). The latter nano-confined ethanol shows a remarkable downfield shift (Δδ = 6.0 ppm) for the methylene group in the solid 13C NMR spectrum compared with that of the free EtOH. Crystal 1 with a regular hexagonal appearance can be used directly for saline water desalination on a small-scale at an ambient temperature, demonstrating a low energy consumption and environmentally friendly method. This is attributed to the 10.0 Å hydrophobic open-channel containing water nanotubes (WNTs, Φ = 4.2 Å). The nano-confined WNTs can be removed at a low temperature (45 °C).

Synthesis, spectral, and structural characterizations of imidazole oxalato molybdenum(IV/V/VI) complexes.

Substitutions of trans-Na(Him)[Mo(2)O(4)(ox)(2)(H(2)O)(2)]·H(2)O (1) and trans-(Him)(2)[Mo(2)O(4)(ox)(2)(H(2)O)(2)] (2) with imidazole result in the formation of the mixed-ligand molybdenum complexes cis-Na(2)[Mo(2)O(4)(ox)(2)(im)(2)]·4.5H(2)O (3), cis-K(2)[Mo(2)O(4)(ox)(2)(im)(2)]·3H(2)O (4), respectively (H(2)ox = oxalic acid; im = imidazole). Further reduction of cis-K(2)[Mo(2)O(4)(ox)(2)(im)(2)]·3H(2)O (4) gives a trinuclear molybdenum(IV) complex K(Him)[Mo(3)O(4)(ox)(3)(im)(3)]·3H(2)O (5), which contains an incomplete cubane cluster [Mo(IV)(3)O(4)](4+). Two novel trinuclear mixed-valence imidazole compounds [Mo(3)O(8)(im)(4)](im)·H(2)O (6) and [Mo(3)O(8)(im)(4)]·H(2)O (7) were obtained by the reduction of (Him)(4)[Mo(8)O(26)(im)(2)] (8). Both 6 and 7 contain a novel Mo(VI)O(4)(Mo(V)(2)O(4)) center, where the [Mo(V)(2)O(4)](2+) unit is linked by [Mo(VI)O(4)](2-) anion. The Mo-Mo bond distances in 1-7 decrease with the decrease of oxidation state of molybdenum. Solid and solution NMR spectra show that imidazole molybdenum compounds 6-8 fully dissociate in solution, where solvated imidazole and imidazolium groups in 6 and 8 could be served as internal references in their solid (13)C NMR spectra. Furthermore, mixed-ligand molybdenum species 3 and 4 are stable in water. Stabilities of 3 and 4 in solution may be attributed to the strong coordination of bidentate oxalate and the formation of hydrogen bond. Dimers 2 and 4 display quasi-reversible redox process, while trimer 6 is irreversible. Bond valence calculations for 1-8 are consistent with their oxidation states of molybdenum atoms. Calculation of the oxidation state in recent structure of iron molybdenum cofactor [MoFe(7)S(9)C(R-homocit)] (FeMo-co) is 3.318.

Methanol triggered ligand flip isomerization in a binuclear copper(I) complex and the luminescence response.

Methanol drives the blue emissive complex, [Cu(2)(dppy)(3)(MeCN)](BF(4))(2) (dppy = diphenylphosphino-pyridine), with a head-to-tail arrangement of the three bridging phosphine ligands to convert to its linkage isomer (head-to-head, green emissive) in the solid state, and the transformation could be reversibly realized through recrystallization in different solvents.

A luminescent gold(I)-copper(I) cluster with unprecedented carbon-centered trigonal prismatic hexagold.

An unprecedented trigonal prismatic (µ(6)-C)Au(6) structure has been found in a novel gold(I)-copper(I) cluster with a hypercoordinated carbon, [CAu(6)Cu(2)(dppy)(6)](BF(4))(4); the incorporation of copper ions enhances the rigidity and integrity of the cluster and turns on the bright red solution luminescence.

N-heterocycle chelated oxomolybdenum(VI and V) complexes with bidentate citrate.

A 1,10-phenanthroline (phen) chelated molybdenum(VI) citrate, [(MoO2)2O(H2cit)(phen)(H2O)2] x H2O (1) (H4cit = citric acid), is isolated from the reaction of citric acid, ammonium molybdate and phen in acidic media (pH 0.5-1.0). A citrato oxomolybdenum(V) complex, [(MoO)2O(H2cit)2(bpy)2] x 4H2O (2), is synthesized by the reduction of citrato molybdate with hydrazine hydrochloride in the presence of 2,2'-bipyridine (bpy), and a monomeric molybdenum(VI) citrate [MoO2(H2cit)(bpy)] x H2O (6) is also isolated and characterized structurally. The citrate ligand in the three neutral compounds uses the alpha-alkoxy and alpha-carboxy groups to chelate as a bidentate leaving the two beta-carboxylic acid groups free, that is different from the tridentate chelated mode in the citrato molybdate(VI and V) complexes. 1 and in solution show obvious dissociation based on 13C NMR studies.

Ligand- and anion-controlled formation of silver alkynyl oligomers from soluble precursors.

Novel silver(I) alkynyl cluster complexes ([Ag5(bpy)4(C [triple bond] CBu(t))2](3+), [Ag8(bpy)6(C [triple bond] CBu(t))4](4+), and [Ag 12(bpy)4(C [triple bond] CBu(t))6(CF3CO2)6]) have been synthesized by reacting soluble polymeric precursors with bipyridine ligands, and control of the nuclearity can be achieved by varying the molar ratio of the reactants and using different types of anions.

Syntheses, spectroscopies and structures of molybdenum(VI) complexes with homocitrate.

Initial investigations into the possible role of homocitric acid in iron molybdenum cofactor (FeMo-co) of nitrogenase lead us to isolate and characterize two tetrameric molybdate(VI) species. The complexes K2(NH4)2[(MoO2)4O3(R,S-Hhomocit)2].6H2O (1) and K5[(MoO2)4O3(R,S-Hhomocit)2]Cl.5H2O (2) (homocitric acid = H4homocit, C7H10O7) are prepared from the reactions of acyclic homocitric acid and molybdates, which represent the first synthetic structural examples of molybdenum homocitrate complexes. The homocitrate ligand trapped by tetranuclear molybdate coordinates to the molybdenum(VI) atom through alpha-alkoxy and alpha-, beta-carboxy groups. The physical properties, structural parameters, and their possible biological relevances are discussed.

Dimeric dioxomolybdenum(VI) and oxomolybdenum(V) complexes with citrate at very low pH and neutral conditions.

A novel dimeric dioxomolybdenum(VI) citrate complex, K[(MoO2)2-(OH)(H2cit)2].4H2O (1), with weak coordination of beta-carboxylic acid groups and the first structural example of an oxomolybdenum(V) citrate complex, (NH4)6[Mo2O4(cit)2].3H2O (2) (H4cit = citric acid), are isolated in a very acidic solution (pH 0.5-1.0) and neutral conditions (pH 7.0-8.0), respectively. Complex 1 displays strong double hydrogen bonds through beta-carboxyl and beta-carboxylic acid groups [2.621(9) A]. Transformations of the dimeric molybdenum(VI) citrate show that protonation of a carboxyl group will weaken the coordination of molybdenum(VI) citrate. There are obvious dissociations of molybdenum(VI/V) citrate complexes based on 13C NMR observations in solution.

Syntheses, crystal structures and biological relevance of glycolato and S-lactato molybdates.

Glycolato and S-lactato complexes containing the dioxomolybdenum(VI) moiety have been synthesized for studies on the role of the alpha-hydroxycarboxylato anion in the iron molybdenum cofactor of nitrogenase. The ligands in these complexes, vis K2[MoO2(glyc)2].H2O (H2glyc=glycolic acid, C2H4O3) (1) and (Na2[MoO2(S-lact)2])3.13H2O (H2lact=lactic acid, C3H6O3) (2) chelate through their alpha-alkoxyl and alpha-carboxyl oxygen atoms. In contrast, octanuclear K6[(MoO2)8(glyc)6(Hglyc)2].10H2O (3) formed by the reduction of the glycolato complex (1), features three different ligand binding modes: (i) non-bridging and bridging bidentate coordination of alpha-alkoxyl and alpha-carboxyl groups, and (ii) bidentate bridging using alpha-carboxyl group, leaving the alpha-alkoxyl group free. The octanuclear skeleton shows strong metal-metal interactions. The coordination modes in (1) and (2) mimic that of homocitrate to the iron molybdenum cofactor (FeMo-co) of nitrogenase. The bidentate coordination of alpha-alkoxyl and alpha-carboxyl groups shows that bond of alpha-carboxyl group to Mo is less susceptible to the oxidation state of molybdenum compared with the Mo-alpha-alkoxyl bond. This is supported by the dinuclear coordination of alpha-carboxyl group with free alpha-alkoxyl group in glycolato molybdate(V) (3).