2.4.2. Interpenetrated Ladders 711 2.4.3. Unusual Motifs of Ladders 713 2.4.4. Properties of Ladderlike Chains 713 2.5. Rotaxane Polymers 714 2.5.1. 1D Polyrotaxanes 714 2.5.2. 2D Polyrotaxanes 715 2.5.3. 3D Polyrotaxanes 716 2.5.4. Hydrogen-Bonded Polyrotaxanes 716 2.6. Ribbon/Tape Polymers 717 2.7. Metal Cluster As Building Blocks for 1D CP 718 2.7.1. Metal Carboxylate Clusters 718 2.7.2. Metal Halide Clusters 719 2.7.3. Metal Chalcogenide Clusters 720 2.7.4. Polyoxometalate Clusters 721 2.7.5. Single Molecular Magnets as Building Blocks 722

One-Dimensional Coordination Polymers: Complexity and Diversity in Structures, Properties, and Applications

ion model is not a true H-abstracting process but rather a special case of proton-coupled electron transfer where reduction of YZ by the Mn4 cluster occurs with the proton emanating from solvent water. These two theories will now be described briefly. A hydrogen atom abstraction process by the YZ residue in conjunction with a dimer-of-dimers structural template has led to an interesting hypothesis wherein an O atom is proposed as a terminal ligand to Mn (see Figure 8 (top)).175,188 The Clion is proposed to migrate in S1 to S2 and S2 to S3 state transitions while YZ serves as the H atom abstractor and Ca2+ ion binds to Clin the lower S states. In another proposal two dinuclear Mn complexes perform diverse functions: one oxidizes H2O to peroxide while the other converts peroxide to water.16,189-191 The final O-O bond forming step in the S4 state is predicted to result from attack of the hydroxo group bound to Ca2+ to a strongly electrophilic MnVdO species. In a similar hypothesis, a Clbridging between a Mn and a Ca2+ is responsible for modulating the nucleophilic attack of the hydroxide ion.181,192 This was first predicted from mass spectrometric studies.176 The product of this step has been argued to be similar to the ferric hydroperoxide in oxyhemerythrin. Oxygen release is envisioned in a manner similar to that of oxyhemerythrin concomitant with reduction of Mn and protonation of μ-oxo bridges.192 On the basis of XAS and EPR data, another mechanism incorporating a “C-shaped” cluster has also been suggested recently involving one redox-active Mn per [Mn2(μ-O)2] dimeric moiety (see Figure 8 (bottom)).17,193,194 Here, the O-O bond is formed between an oxyl radical and a μ-oxo atom. A hybrid density functional theory has been utilized to put forward a triangular Mn moiety closely coupled by μ-oxo groups as a potential model for the WO site. The previously suggested oxyl radical mechanism14 has been reexamined in this work with an oxyl radical placed in a bridging fashion between two Mn atoms. Consistent with earlier studies, only one Mn is redox active in this model and the Ca2+ ion has been shown as playing the role of a bridging metal Manganese Clusters with Relevance to Photosystem II Chemical Reviews, 2004, Vol. 104, No. 9 3991

Manganese clusters with relevance to photosystem II.

Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates: Synthesis, Structure, Transformations, and Applications

A series of new metal–organic frameworks (MOFs), [Zn(1,2-pda)(bipy)(H2O)2]n (1), [Zn(1,3-pda) (bipy)(H2O)]n·nH2O (2), [Zn(1,4-pda)(bipy)]n·nCH3OH (3), [Zn(1,2-pda)(dpe)]n·3nH2O (4), and [Zn(1,3-pda)(bpa)]n·2nH2O (5) [H2pda = phenylenediacetic acid, bipy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)ethylene, bpa = 1,2-bis(4-pyridyl)ethane] have been synthesized and structurally characterized. The structure determination reveals that complex 1 is a 2D layered network and exhibits a typical (4,4) topological net, which further assembles into a 3D two-fold interpenetrated pcu topology when hydrogen bonding interactions are considered. Complex 2 shows a 2D (5,2)-connected topological network via hydrogen bonding interactions based on the 1D double-chains. For complex 3, when the 1,4-pda ligands act as a three-connected node, the 2D double-layered structure displays a unique (5,3)-connected topology with a Schlafli symbol (42,67,8)(42,6). Complex 4 features a rare 3D three-fold interpenetrated diamondoid framework (dia, 66 topology) with (2.2.1) Hopf links and (6.3.3) Torus links, and the helical water chains are encased in the 1D neighboring channels. Complex 5 is a 2D corrugated net with a Schlafli symbol (44,62), and the puckered nature of the layers assembles them to interpenetrate in an unusual 2D → 3D parallel fashion. Particularly, a discrete tetramer water cluster, (H2O)4, is located in the crystal lattice of 5. The structural differences demonstrate that the backbones of the phenylenediacetic acids are a key point to form the final metal–ligand coordination polymers. Moreover, the fluorescent properties of complexes 1–5 were studied in the solid state at room temperature.

A series of Zn(II) coordination complexes derived from isomeric phenylenediacetic acid and dipyridyl ligands: syntheses, crystal structures, and characterizations

https://www.rsc.org/suppdata/cc/c0/c0cc01804j/c0cc01804j.pdf

Spontaneous resolution upon crystallization of chiral La(III) and Gd(III) MOFs from achiral dihydroxymalonate

Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta-D-gluconolactone, D-glucuronic acid, or D-glucaric acid in dimethylformamide resulted in the formation of discrete tetracopper complexes with sugar acids, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-SA)2(bpy)4](NO3)2 [SA = D-gluconate (6), D-glucuronate (7), D-glucarateH (8a)]. The structures of 6 and 7 were determined by X-ray crystallography to be almost identical with that of 3 with additional chelating coordination of the C-2 hydroxyl group of D-gluconate moieties (6) or the C-5 cyclic O atom of D-glucuronate units (7). Those with D-glucaric acid and D-lactobionic acid afforded chiral one-dimensional polymers, {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-glucarate)(bpy)4](NO3)2}n (8b) and {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-lactobionate)(bpy)4(H2O)2](NO3)3}n (9), respectively, in which the D-Glc-1P-bridged tetracopper(II) units are connected by sugar acid moieties through the C-1 and C-6 carboxylate O atoms in 8b and the C-1 carboxylate and C-6 alkoxy O atoms of the gluconate chain in 9. When complex 7 containing d-glucuronate moieties was heated in water, the mononuclear copper(II) complex with 2-dihydroxy malonate, [Cu(mu-O2CC(OH)2CO2)(bpy)] (10), and the dicopper(II) complex with oxalate, [Cu2(mu-C2O4)(bpy)2(H2O)2](NO3)2 (11), were obtained as a result of oxidative degradation of the carbohydrates through C-C bond cleavage reactions.

Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

Reactions of CuX2·nH2O with the biscarboxylate ligand XDK (H2XDK = m-xylenediamine bis(Kemp's triacid imide)) in the presence of N-donor auxiliary ligands yielded a series of dicopper(II) complexes, [Cu2(μ-OH)(XDK)(L)2]X (L = N,N,N‘,N‘-tetramethylethylenediamine (tetmen), X = NO3 (1a), Cl (1b); L = N,N,N‘-trimethylethylenediamine (tmen), X = NO3 (2a), Cl (2b); L =2,2‘-bipyridine (bpy), X = NO3 (3); L = 1,10-phenanthroline (phen), X = NO3 (4); L = 4,4‘-dimethyl-2,2‘-bipyridine (Me2bpy), X = NO3 (5); L = 4-methyl-1,10-phenanthroline (Mephen), X = NO3 (6)). Complexes 1−6 were characterized by X-ray crystallography (Cu···Cu = 3.1624(6)−3.2910(4) A), and the electrochemical and magnetic properties were also examined. Complexes 3 and 4 readily reacted with diphenyl phosphoric acid (HDPP) or bis(4-nitrophenyl) phosphoric acid (HBNPP) to give [Cu2(μ-phosphate)(XDK)(L)2]NO3 (L = bpy, phosphate = DPP (11); L = phen, phosphate = DPP (12), BNPP (13)), where the phsophate diester bridges the two copper ions in a μ-1,3...

Dinuclear copper(II) complexes with (Cu2(μ-hydroxo)bis(μ-carboxylato)}+ cores and their reactions with sugar phosphate esters : A substrate binding model of fructose-1,6-bisphosphatase

Reactions of MnX2·nH2O with tris(N-(d-mannosyl)-2-aminoethyl)amine ((d-Man)3-tren), which was formed from d-mannose and tris(2-aminoethyl)amine (tren) in situ, afforded colorless crystals of [Mn((d-Man)3-tren)]X2 (3a, X = Cl; 3b, X = Br; 3c, X = NO3; 3d, X = 1/2SO4). The similar reaction of MnSO4·5H2O with tris(N-(l-rhamnosyl)-2-aminoethyl)amine ((l-Rha)3-tren) gave [Mn((l-Rha)3-tren)]SO4 (4d), where l-rhamnose is 6-deoxy-l-mannose. The structures of 3b and 4d were determined by X-ray crystallography to have a seven-coordinate Mn(II) center ligated by the N-glycoside ligand, (aldose)3-tren, with a C3 helical structure. Three d-mannosyl residues of 3b are arranged in a Δ(ob3) configuration around the metal, leading to formation of a cage-type sugar domain in which a water molecule is trapped. In 4d, three l-rhamnosyl moieties are in a Δ(lel3) configuration to form a facially opened sugar domain on which a sulfate anion is capping through hydrogen bonding. These structures demonstrated that a configurationa...

Novel MnIIMnIIIMnII Trinuclear Complexes with Carbohydrate Bridges Derived from Seven-Coordinate Manganese(II) Complexes with N-Glycoside

A new heptadentate N6−O1 ligand, N,N,N‘,N‘-tetrakis(2-quinolylmethyl)-2-hydroxy-1,3-propanediamine (Htqhpn), was synthesized and used to generate compounds with linearly ordered MnIIMnIIIMnIIIMnII tetranuclear cores This is the lowest valent tetranuclear manganese complex that exhibits a (μ2-O)2Mn2 core in the molecule The electron paramagnetic resonance and magnetic measurements of these tetranuclear complexes suggest moderately strong antiferromagnetic coupling for the central MnIII2 core, with weak coupling between the MnII and MnIII centers

Masahiro Mikuriya

Papers

Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

Dinuclear copper(II) complexes with (Cu2(μ-hydroxo)bis(μ-carboxylato)}+ cores and their reactions with sugar phosphate esters : A substrate binding model of fructose-1,6-bisphosphatase

Novel MnIIMnIIIMnII Trinuclear Complexes with Carbohydrate Bridges Derived from Seven-Coordinate Manganese(II) Complexes with N-Glycoside

N,N,N‘,N‘-Tetrakis(2-quinolylmethyl)-2-hydroxy-1,3-propanediamine (Htqhpn) as a Supporting Ligand for a Low-Valent (μ-O)2 Tetranuclear Manganese Core