Selective Crystallization of Linkage Isomers, [RhIII(NCS)(SCN)5]3- and [RhIII(SCN)6]3-, to Investigate Structural Trans Influence and Thermal Stability.

Linkage isomers of homoleptic complexes, [RhIII(SCN)6]3- and [RhIII(NCS)(SCN)5]3-, formed in aqueous solution were successfully separated by employing methyltriphenylphosphonium (MePPh3+) and 1-ethylquinolinium (EtQu+) ions as countercations, respectively. The single-crystal X-ray analysis of (MePPh3)3[RhIII(SCN)6] (1) indicated that all of the SCN- ligands coordinate to the RhIII ion by S atoms with an octahedral symmetry, where the average bond length of Rh-S is 2.374(7) Å. On the other hand, the RhIII ion of (EtQu)3[RhIII(NCS)(SCN)5]·H2O (2) is coordinated by five S atoms and one N atom of the SCN- ligands with a C4v symmetry. Structural trans influence was observed in the shorter bond length of Rh-S at the trans position of Rh-N. The Rh-S bond length is 2.3398(13) Å significantly shorter than those of 1 by ca. 0.04 Å, although DFT calculations based on the crystal structures indicated that the effective bond order of Rh-N is higher than those of Rh-S. Thermal stability examination by thermogravimetric and differential thermal analyses (TG/DTA) and IR spectroscopy indicated that the linkage isomerization of [RhIII(SCN)6]3- to [RhIII(NCS)(SCN)5]3- proceeded after melting around 174 °C. These results clearly indicate that [RhIII(NCS)(SCN)5]3- is thermodynamically more stable than [RhIII(SCN)6]3- in solid states, although further linkage isomerization hardly occurs.

Heterogenous CO2 Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins.

Transparent and grain boundary-free substrates are essential to immobilize molecular photocatalysts for efficient photoirradiation reactions without unexpected light scattering and absorption by the substrates. Herein, membranes of coordination polymer glass immobilizing metalloporphyrins were examined as a heterogeneous photocatalyst for carbon dioxide (CO2) reduction under visible-light irradiation. [Zn(HPO4)(H2PO4)2](ImH2)2 (Im = imidazolate) liquid containing iron(III) 5,10,15,20-tetraphenyl-21H,23H-porphine chloride (Fe(TPP)Cl, 0.1-0.5 w/w%) was cast on a borosilicate glass substrate, followed by cooling to room temperature, resulting in transparent and grain boundary-free membranes with the thicknesses of 3, 5, and 9 µm. The photocatalytic activity of the membranes was in proportion to the membrane thickness, indicating that Fe(TPP)Cl in the subsurface of membranes effectively absorbed light and contributed to the reactions. The membrane photocatalysts were intact during the photocatalytic reaction and showed no recrystallization or leaching of Fe(TPP)Cl.

Synergistic Effect of FeII and MnII Ions in Cyano-Bridged Heterometallic Coordination Polymers on Catalytic Selectivity of Benzene Oxygenation to Phenol.

A cyano-bridged heterometallic coordination polymer with partial deficiencies of CN- ligands, [MnII(H2O)8/3]3/2[FeII(CN)5(NH3)], forms open metal sites both on MnII and FeII ions by liberation of monodentate ligands such as NH3 and H2O. [MnII(H2O)8/3]3/2[FeII(CN)5(NH3)] exhibits high catalytic activity and selectivity of benzene oxygenation to phenol in the presence of m-chloroperoxybenzoic acid as an oxidant. The postcatalytic spectroscopy of [MnII(H2O)8/3]3/2[FeII(CN)5(NH3)] and catalysis comparison with a physical mixture of [MnII(H2O)3]2[FeII(CN)6] and [Fe(H2O)3/2]4/3[Fe(CN)6], which has open metal sites on both MnII and Fe ions separately, indicated that the high activity resulted from high oxidation ability and phenol adsorption ability of FeII and MnII ions, respectively.

Coordination polymer-forming liquid Cu(2-isopropylimidazolate).

The structure of the melt state of one-dimensional (1D) coordination polymer crystal Cu(isopropylimidazolate) (melting temperature T m = 143 °C) was characterized by DSC, variable temperature PXRD, solid-state NMR (SSNMR), viscoelastic measurements, XAS, and DFT-AIMD calculations. These analyses suggested "coordination polymer-forming liquid" formation with preserved coordination bonds above T m. Variable chain configurations and moderate cohesive interaction in adjacent chains are the keys to the rarely observed polymer-forming liquid. The melt structure is reminiscent of the common 1D organic polymer melts such as entanglement or random coil structures.

Single Open Sites on FeII Ions Stabilized by Coupled Metal Ions in CN-Deficient Prussian Blue Analogues for High Catalytic Activity in the Hydrolysis of Organophosphates.

CN-deficient Prussian blue analogues (PBAs), [MN(H2O)x]y[FeII(CN)5(NH3)] (MN = CuII, CoII, or GaIII), were synthesized and examined as a new class of heterogeneous catalysts for hydrolytic decomposition of organophosphates often used as pesticides. The active species of the CN-deficient PBAs were mainly C-bound FeII ions with only single open sites generated by liberation of the NH3 ligand during the catalytic reactions. [CuII(H2O)8/3]3/2[FeII(CN)5(NH3)] showed higher catalytic activity than [CoII(H2O)8/3]3/2[FeII(CN)5(NH3)] and [GaIII(H2O)][FeII(CN)5(NH3)], although N-bound CuII species has been reported as less active than CoII and GaIII species in conventional PBAs. IR measurements of a series of the CN-deficient PBAs after the catalytic reactions clarified that a part of the NH3 ligands remained on [CoII(H2O)8/3]3/2[FeII(CN)5(NH3)] and that hydrogen phosphate formed as a product strongly adsorbed on the FeII ions of [GaIII(H2O)][FeII(CN)5(NH3)]. Hydrogen phosphate also adsorbed, but weakly, on the FeII ions of [CuII(H2O)8/3]3/2[FeII(CN)5(NH3)]. These results suggest that heterogeneous catalysis of the FeII ions with single open sites were tuned by the MN ions through metal-metal interaction.

Single-Crystal-to-Single-Crystal Installation of Ln4 (OH)4 Cubanes in an Anionic Metallosupramolecular Framework.

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K6 [Rh4 Zn4 O(l-cys)12 ] (K6 [1]; l-H2 cys=l-cysteine) in a water/ethanol solution containing Ln(OAc)3 (Ln3+ =lanthanide ion) results in the exchange of K+ by Ln3+ with retention of the single crystallinity, producing Ln2 [1] (2Ln ) and Ln0.33 [Ln4 (OH)4 (OAc)3 (H2 O)7 ][1] (3Ln ) for early and late lanthanides, respectively. While the Ln3+ ions in 2Ln exist as disordered aqua species, those in 3Ln form ordered hydroxide-bridged cubane clusters that connect [1]6- anions in a 3D metal-organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts.

Creation and stabilisation of tuneable open metal sites in thiocyanato-bridged heterometallic coordination polymers to be used as heterogeneous catalysts.

A series of thiocyanato-bridged heterometallic coordination polymers with a 3D reticular network have been synthesised by the reaction of [PtIV(SCN)6]2- with MII ions to form {MII[PtIV(SCN)6]}n and {[MII(CH3OH)2][PtIV(SCN)6]}n (MII = MnII, FeII, CoII, NiII or CuII) in water and methanol, respectively. Single-crystal X-ray analyses revealed the absence of open metal sites in {MII[PtIV(SCN)6]}ns and the formation of potential open metal sites at the MII ions of {[MII(CH3OH)2][PtIV(SCN)6]}ns by the coordination of methanol. One of the two coordinating methanol molecules in {[CoII(CH3OH)2][PtIV(SCN)6]}n was replaced with pyridine to stabilise the open metal sites, because the methanol molecules are too labile to maintain open metal sites in water. The heterogeneous catalysis of coordination polymers with and without open metal sites was examined for organophosphate hydrolysis and photocatalytic water oxidation to clarify the requisites for heterogeneous catalysts.

Crystal Engineering of Self-Assembled Porous Protein Materials in Living Cells.

Crystalline porous materials have been investigated for development of important applications in molecular storage, separations, and catalysis. The potential of protein crystals is increasing as they become better understood. Protein crystals have been regarded as porous materials because they present highly ordered 3D arrangements of protein molecules with high porosity and wide range of pore sizes. However, it remains difficult to functionalize protein crystals in living cells. Here, we report that polyhedra, a natural crystalline protein assembly of polyhedrin monomer (PhM) produced in insect cells infected by cypovirus, can be engineered to extend porous networks by deleting selected amino acid residues located on the intermolecular contact region of PhM. The adsorption rates and quantities of fluorescent dyes stored within the mutant crystals are increased relative to those of the wild-type polyhedra crystal (WTPhC) under both in vitro and in vivo conditions. These results provide a strategy for designing self-assembled protein materials with applications in molecular recognition and storage of exogenous substances in living cell as well as an entry point for development of bioorthogonal chemistry and in vivo crystal structure analysis.

Photoactivatable CO release from engineered protein crystals to modulate NF-κB activation.

Photoactivatable CO releasing protein crystals were developed by immobilization of Mn carbonyl complexes in polyhedral crystals, which are spontaneously formed in insect cells. The photoactivatable CO release from the engineered protein crystals activates nuclear factor kappa B (NF-κB) upon stimulation by visible light irradiation with suppression of cytotoxicity of the Mn complex.

Preparation of a cross-linked porous protein crystal containing Ru carbonyl complexes as a CO-releasing extracellular scaffold.

Protein crystals generally are stable solid protein assemblies. Certain protein crystals are suitable for use as nanovessels for immobilizing metal complexes. Here we report the preparation of ruthenium carbonyl-incorporated cross-linked hen egg white lysozyme crystals (Ru·CL-HEWL). Ru·CL-HEWL retains a Ru carbonyl moiety that can release CO, although a composite of Ru carbonyl-HEWL dissolved in buffer solution (Ru·HEWL) does not release CO. We found that treatment of cells with Ru·CL-HEWL significantly increased nuclear factor kappa B (NF-κB) activity as a cellular response to CO. These results demonstrate that Ru·CL-HEWL has potential for use as an artificial extracellular scaffold suitable for transport and release of a gas molecule.

Porous protein crystals as catalytic vessels for organometallic complexes.

Porous protein crystals, which are protein assemblies in the solid state, have been engineered to form catalytic vessels by the incorporation of organometallic complexes. Ruthenium complexes in cross-linked porous hen egg white lysozyme (HEWL) crystals catalyzed the enantioselective hydrogen-transfer reduction of acetophenone derivatives. The crystals accelerated the catalytic reaction and gave different enantiomers based on the crystal form (tetragonal or orthorhombic). This method represents a new approach for the construction of bioinorganic catalysts from protein crystals.

Artificial metalloenzymes constructed from hierarchically-assembled proteins.

The design of artificial metalloenzymes has become an important topic in biological chemistry and inorganic chemistry due to the potential applications of artificial metalloenzymes in nanoscience and biotechnology. One of the general methods used to produce artificially metalloenzymes involves the encapsulation of non-natural metal cofactors within protein scaffolds. This method has been used in the construction of small artificial metalloproteins with high activity and selectivity. However, the important roles of protein assemblies have not yet been systematically investigated in this field, even though natural enzymatic systems employ protein assemblies as molecular scaffolds for elaborate enzymatic reactions. In recent years, the above-mentioned general strategy has been applied to functionalize protein assemblies such as protein cages and protein crystals. These assembled structures form confined interior environments, which can be used to accommodate metal complex catalysts and to prepare metal nanoparticles. The development of artificial metalloenzymes with hierarchically-assembled proteins would enable us to provide powerful tools for industrial and biological applications. In this Focus Review, we discuss the most significant recent research in this field as well as future directions.