Two novel 3D borates: porous-layer and layer-pillar frameworks.

Two new borates, NaK[B{BO(OH)}{BO(OH)}] (1) and Na[Al{BO(OH)}{BO}{BO(OH)}] (2), have been made by a solvothermal method. Structure 1 is made of two types of oxoboron clusters ([BO(OH)] and [BO(OH)]) and BO tetrahedra to form a 3D porous layer, in which the [BO(OH)] clusters are bridged by BO groups to produce a 2D B-O layer with 11-membered ring (MR) windows, while the [BO(OH)] clusters as 2-connected pillars join the adjacent B-O layers to make a 3-D porous layer. Structure 2 is built from two types of oxoboron clusters ([BO(OH)] and [BO]), AlO units and BO(OH) triangles to produce 3D pillar-layered aluminoborate (ABO), in which the [BO] clusters are linked together to form a 2-D B-O layer; the [BO(OH)] clusters and AlO groups join each other to form 1D tubular ABO; and the BO(OH) triangles act as linkers to connect the adjacent B-O layer and the ABO tubes, resulting in 3D pillar-layered ABO.

A family of novel Mn₃Ln₄ clusters displaying single-molecule magnet behavior.

Using 3-methyloxysalicylaldoxime (mosaoH2) and N-methyl diethanolamine (N-mdeaH2) as coligands, a family of heptanuclear Mn/Ln heterometallic compounds [Mn(II)Mn(III)2Ln(III)4(mosao)2(mosaoH)4(piv)4(N-mdea)4]·xMeCN [Ln = Dy(1), Tb(2) and Y(3), pivH = pivalic acid] have been prepared. The crystal structures of 1-3 were obtained, and their core consists of two Mn(III)Ln2(μ3-OR)2 (RO(2-) = N-mdea(2-)) triangles linked to a central Mn(II) atom. A dc magnetic susceptibility study reveals that single-ion effects of the Ln ions are dominant in compounds 1 and 2.

Efficient photo-driven hydrogen evolution by binuclear nickel catalysts of different coordination in noble-metal-free systems.

Exploration of the complex Ni2(MBD)4 (MBD = 2-mercaptobenzimidazole) (C1) having different coordinated Ni atoms as a photocatalyst for hydrogen evolution is made. For comparison, the bimetallic Ni2(MBT)4 (MBT = 2-mercaptobenthiazole) (C2) complex with the same coordinated Ni atoms was synthesized. Both of the complexes have been successfully constructed for photo-induced hydrogen production using organic dyes as photosensitizers and triethanolamine (TEOA) as the effective electron donor by visible light (>400 nm) in acetonitrile-water solution.

Octanuclear Mn(III)6Mn(II)Ln (Ln = Gd, Dy and Er) clusters with a novel core topology: syntheses, structures, and magnetic properties.

Reactions of [Mn6O2(piv)10(py)2.5(piv)1.5], Ln(NO3)3·6H2O and N-mdeaH2 in MeCN in the presence of Me3SiCl generated a family of octanuclear Mn/Ln complexes [Mn6(III)Mn(II)Ln(N-mdea)3(N-mdeaH)(piv)8O2(OH)3(NO3)(H2O)]·xCH3CN·xH2O [Ln = Gd (1), Dy (2), Er (3), pivH = pivalic acid, N-mdeaH2 = N-methyl diethanolamine].

Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution.

Two [FeFe] hydrogenase mimics, [Fe(2)(μ-pdt)(CO)(5)L1] (L1 = PPh(2)SPhNH(2)) (Ph = phenyl) (2) and [Fe(2)(μ-pdt)(CO)(5)L2] (L2 = PPh(2)PhNH(2)) (3), and two molecular photocatalysts, [(CO)(5)(μ-pdt)Fe(2)PPh(2)SPhNHCO(bpy)(ppy)(2)Ir]PF(6) (bpy = bipyridine, ppy = 2-phenylpyridine) (2a) and [(CO)(5)(μ-pdt)Fe(2)PPh(2)PhNHCO(bpy)(ppy)(2)Ir](PF(6)) (3a), have been designed and synthesized, anchoring Ir(ppy)(2)(mbpy)PF(6) (mbpy = 4-methyl-4'-carbonyl-2,2'-bipyridine) (PS) to one of the iron centers of complexes 2 and 3 by forming amide bonds. Molecular dyads 2a, 3a and the intermolecular systems 2, 3 with PS have also been successfully constructed for photoinduced H(2) production using triethylamine (TEA) as a sacrificial electron donor by visible light (>400 nm) in CH(3)CN-H(2)O solution. The time-dependence of H(2) generation and spectroscopic studies suggest that the activity of H(2) evolution can be tuned by addition of a S atom to the phosphane ligand.

Syntheses, structures, and magnetic properties of a family of tetra-, hexa-, and nonanuclear Mn/Ni heterometallic clusters.

A family of Mn(III)/Ni(II) heterometallic clusters, [Mn(III)(4)Ni(II)(5)(OH)(4)(hmcH)(4)(pao)(8)Cl(2)]·5DMF (1·5DMF), [Mn(III)(3)Ni(II)(6)(N(3))(2)(pao)(10)(hmcH)(2)(OH)(4)]Br·2MeOH·9H(2)O (2·2MeOH·9H(2)O), [Mn(III)Ni(II)(5)(N(3))(4)(pao)(6)(paoH)(2)(OH)(2)](ClO(4))·MeOH·3H(2)O (3·MeOH·3H(2)O), and [Mn(III)(2)Ni(II)(2)(hmcH)(2)(pao)(4)(OMe)(2)(MeOH)(2)]·2H(2)O·6MeOH (4·2H(2)O·6MeOH) [paoH = pyridine-2-aldoxime, hmcH(3) = 2, 6-Bis(hydroxymethyl)-p-cresol], has been prepared by reactions of Mn(II) salts with [Ni(paoH)(2)Cl(2)], hmcH(3), and NEt(3) in the presence or absence of NaN(3) and characterized. Complex 1 has a Mn(III)(4)Ni(II)(5) topology which can be described as two corner-sharing [Mn(2)Ni(2)O(2)] butterfly units bridged to an outer Mn atom and a Ni atom through alkoxide groups. Complex 2 has a Mn(III)(3)Ni(II)(6) topology that is similar to that of 1 but with two corner-sharing [Mn(2)Ni(2)O(2)] units of 1 replaced with [Mn(3)NiO(2)] and [MnNi(3)O(2)] units as well as the outer Mn atom of 1 substituted by a Ni atom.

(6-Oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylato-κ2O5,O6)bis[2-(2-pyridyl)-1H-benzimidazole-κ2N2,N3]manganese(II) monohydrate.

In the title compound, [Mn(C(5)H(2)N(2)O(4))(C(12)H(9)N(3))(2)]·H(2)O, the Mn(II) centre is surrounded by three bidentate chelating ligands, namely, one 6-oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylate (or uracil-5-carboxylate, Huca(2-)) ligand [Mn-O = 2.136 (2) and 2.156 (3) Å] and two 2-(2-pyridyl)-1H-benzimidazole (Hpybim) ligands [Mn-N = 2.

Synthesis, structures and electrochemistry studies of 2Fe2S-Fe(ii)(S-2N)(2) models for H-cluster of [FeFe]-hydrogenase.

A series of model complexes [(μ-pdt)Fe(2)(CO)(5)](2)M(sip)(2) (M = Fe, Ni) were synthesized as H-cluster analogues of [FeFe]-hydrogenase. Their electrochemical behaviours were investigated and it is proposed that the bridging metal bis(tris-chelate) groups act as electron transfer sites in theses mimics.

The use of phosphonates for constructing 3d-4f clusters at high oxidation states: synthesis and characterization of two unusual heterometallic CeMn complexes.

The use of phosphonic acids in the synthesis of mixed-metal CeMn complexes has led to the formation of two phosphonate complexes with unusual topologies: [Ce(2)Mn(6)O(6)(OH)(5)(t-BuPO(3))(6)(O(2)CMe)(3)] x 53 H(2)O (1 x 53 H(2)O) and [Ce(22)Mn(12)O(34)(MePO(3))(12)(O(2)CMe)(33)(OMe)(6)(NO(3))(H(2)O)(12)](n) (2). The two mixed-metal CeMn complexes were both prepared from a reaction system containing Mn(O(2)CMe)(2) and (NH(4))(2)[Ce(NO(3))(6)] with similar procedures except for using different phosphonic acids (tert-butylphosphonic acid and methylphosphonic acid, respectively) as coligands. Both complexes possess rare topology of triangular type, with compound 1 being a 0D discrete cluster, whereas, compound 2 is a 1D polymer.

Synthesis and characterization of a family of penta- and tetra-manganese(III) complexes derived from an assembly system containing tert-butylphosphonic acid.

A family of manganese complexes, [Mn 5O 3( t-BuPO 3) 2(MeCOO) 5(H 2O)(phen) 2] ( 1), [Mn 5O 3( t-BuPO 3) 2(PhCOO) 5(phen) 2] ( 2), [Mn 4O 2( t-BuPO 3) 2(RCOO) 4(bpy) 2] (R = Me, ( 3); R = Ph, ( 4)), NBu (n) 4[Mn 4O 2(EtCOO) 3(MeCOO) 4(pic) 2] ( 5), NR' 4[Mn 4O 2( i-PrCOO) 7(pic) 2] (R' = Bu (n) , ( 6); R' = Et, ( 7)), were synthesized and characterized. The seven manganese clusters were all prepared from a reaction system containing tert-butylphosphonic acid, Mn(O 2CR) 2 (R = Me, Ph) and NR' 4MnO 4 (R' = Bu (n) , Et) with similar procedures except for using different N-containing ligands (1,10-phenanthroline (phen), 2,2'-bipyridine (bpy) and picolinic acid (picH)) as coligands. The structures of these complexes vary with the N-containing donors.

[2-(2-Pyridyl)-1H-benzimidazole-kappa2N2,N3]bis(p-toluato-kappa2O,O')manganese(II).

In the title compound, [Mn(C8H7O2)2(C12H9N3)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2-(2-pyridyl)benzimidazole ligand [Mn-N = 2.1954 (13) and 2.2595 (14) A] and two p-toluate ligands [Mn-O = 2.

Aqua(dipicolinato-kappa(3)O,N,O')(1H-imidazole-kappaN(3))(1,10-phenanthroline-N,N')manganese(II).

In the title compound, [Mn(C(7)H(3)NO(4))(C(3)H(4)N(2))(C(12)H(8)N(2))(H(2)O)], the Mn(II) centre is surrounded by one bidentate phenanthroline ligand [Mn-N = 2.383 (3) and 2.421 (3) A], one tridentate dipicolinate ligand [Mn-N = 2.

Diiron models for the active site of Fe-only hydrogenase with terminal organosulfur ligation: synthesis, structures and electrochemistry.

Diiron model complexes (micro-SCH(2)CH(2)CH(2)S)Fe(2)(CO)(5)L with thioether-substitution, L=S(CH(2)CH(3))(2) (2), S(CH(2)CH(3))(CH(2)CH(2)Cl) (3), S(CH(2)CH(3))(C(6)H(5)) (4), or sulfoxide-substitution, L=SO(CH(2)CH(2)CH(3))(2) (5), SO(CH(3))(2) (6), were synthesized as active site analogues of Fe-only hydrogenase. The organosulfur ligands were introduced into the diiron centers via moderately stable intermediates following two routes. The X-ray crystallographic structures of complexes 2-6 show the apical positions of terminal organosulfur ligands.

catena-Poly[[aqua(2,2'-bipyridine-kappa2N,N')manganese(II)]-mu-terephthalato-kappa3O,O':O"].

The title complex, [Mn(C(8)H(4)O(4))(C(10)H(8)N(2))(H(2)O)](n), takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn(II) center is surrounded by two tp ligands, one water molecule and one 2,2'-bipyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.

Poly[[[aquamanganese(II)]-mu2-4,4'-bipyridine-mu3-succinato] 4,4'-bipyridine hemisolvate].

The polymeric title complex, [[Mn(C(4)H(4)O(4))(C(10)H(8)N(2))(H(2)O)].0.5C(10)H(8)N(2)](n), possesses a three-dimensional open-framework structure, with the solvate 4,4'-bipyridine (bipy) molecules, which lie around centers of inversion, clathrated in the channels of the framework.