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Themed collection Coordination Programming: Science of Molecular Superstructures Towards Chemical Devices

58 articles
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Front cover

Graphical abstract: Front cover
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Graphical abstract: Inside front cover
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Graphical abstract: Back cover
Editorial

Coordination programming: science of molecular superstructures towards chemical devices

Welcome to this themed issue of Dalton Transactions entitled “Coordination Programming: Science of Molecular Superstructures Towards Chemical Devices”.

Graphical abstract: Coordination programming: science of molecular superstructures towards chemical devices
Open Access Perspective

Long-lived photoinduced charge separation for solar cell applications in supramolecular complexes of multi-metalloporphyrins and fullerenes

We review photoinduced charge separation in surpramolecular complexes of porphyrins and fullerenes, towards construction of suparamolecular solar cells based on the long-lived photoinduced charge separation.

Graphical abstract: Long-lived photoinduced charge separation for solar cell applications in supramolecular complexes of multi-metalloporphyrins and fullerenes
Open Access Perspective

Fluorescent azobenzenes and aromatic aldimines featuring an N–B interaction

The N–B interaction makes azobenzenes and aromatic aldimines fluorescent, and their properties change in response to protons, electrons, and ions.

Graphical abstract: Fluorescent azobenzenes and aromatic aldimines featuring an N–B interaction
Perspective

Sequential growth at the sub-10 nm scale of cyanide bridged coordination networks on inorganic surfaces

The elaboration of coordination networks’ nano-objects on surfaces can be realized by sequential growth in solution (SGS).

Graphical abstract: Sequential growth at the sub-10 nm scale of cyanide bridged coordination networks on inorganic surfaces
Open Access Communication

Bottom-up assembly of ultrathin sub-micron size metal–organic framework sheets

Highly-crystalline ultrathin metal–organic framework nanosheets with sub-micron planar size were created by a solution-based two-dimensional interfacial reaction.

Graphical abstract: Bottom-up assembly of ultrathin sub-micron size metal–organic framework sheets
Open Access Communication

Oxo-carboxylato-molybdenum(VI) complexes possessing dithiolene ligands related to the active site of type II DMSOR family molybdoenzymes

Oxo-carboxylato-molybdenum(VI) complexes are generated as models of the active site of type II DMSOR family of molybdoenzymes.

Graphical abstract: Oxo-carboxylato-molybdenum(vi) complexes possessing dithiolene ligands related to the active site of type II DMSOR family molybdoenzymes
Communication

Cross-linked conjugated polymer assemblies at the air–water interface through supramoleculer bundling

Cross-linked conjugated polymer assemblies by host–guest interaction were developed at the air–water interface by means of the Langmuir–Blodgett technique.

Graphical abstract: Cross-linked conjugated polymer assemblies at the air–water interface through supramoleculer bundling
Communication

A facile and versatile approach to efficient enhancement of solid-state luminescence by organic–inorganic hybrid salts

Organic–inorganic hybrid salts were one of the effective approaches to overcome aggregation-induced quenching in the crystalline state.

Graphical abstract: A facile and versatile approach to efficient enhancement of solid-state luminescence by organic–inorganic hybrid salts
Communication

Palladium- or proton-induced submicro spherical aggregation of macrocyclic amphiphiles in aqueous solution

Hexaaza-cyclophane ligands which are protonated and palladated with [Pd(en)]2+ form submicrometre-sized spherical aggregates in water.

Graphical abstract: Palladium- or proton-induced submicro spherical aggregation of macrocyclic amphiphiles in aqueous solution
Communication

A highly-active and poison-tolerant Pt12 sub-nanocluster catalyst for the reductive amination of aldehydes with amines

A Pt12 sub-nanocluster catalyst supported by graphitized mesoporous carbon has been prepared, exhibiting a remarkable catalytic activity in reductive amination. In addition, we revealed that the catalysts have a remarkable poison-tolerance.

Graphical abstract: A highly-active and poison-tolerant Pt12 sub-nanocluster catalyst for the reductive amination of aldehydes with amines
Communication

Relative anion binding affinity in a series of interpenetrated coordination cages

The affinity of four interpenetrated cages for the binding of chloride and bromide in their outer two pockets is compared experimentally and supported by theoretical methods.

Graphical abstract: Relative anion binding affinity in a series of interpenetrated coordination cages
Communication

Spontaneous electrodeposition of gold and platinum complexes through a coronene adlayer on Au(111)

Spontaneous electrodeposition of AuBr4 and PtBr42− occurred at the coronene adlayer formed on the reconstructed Au(111) surface.

Graphical abstract: Spontaneous electrodeposition of gold and platinum complexes through a coronene adlayer on Au(111)
Communication

Modification of charge transfer in a two-dimensional donor/acceptor framework by the insertion of another donor-type molecule into electronegative interlayer pockets

Pyrene-intercalated layered compounds, [{Ru2(O2CCF3)4}2(TCNQRx)]·2(pyrene) (TCNQRx = 7,7,8,8-tetracyano-p-quinodimethane derivatives; Rx = H4 and F4), were synthesized.

Graphical abstract: Modification of charge transfer in a two-dimensional donor/acceptor framework by the insertion of another donor-type molecule into electronegative interlayer pockets
Communication

Guest responsivity of a two-dimensional coordination polymer incorporating a cholesterol-based co-ligand

A new two-dimensional Hofmann-type coordination polymer incorporating a hydrophobic cholesterol-based co-ligand showed a unique guest response.

Graphical abstract: Guest responsivity of a two-dimensional coordination polymer incorporating a cholesterol-based co-ligand
Communication

Ternary metal Prussian blue analogue nanoparticles as cathode materials for Li-ion batteries

A ternary metal Prussian blue analogue was applied as cathode material for Li-ion batteries. Heterometal substitution led to both a longer cycle life and a higher rate capability.

Graphical abstract: Ternary metal Prussian blue analogue nanoparticles as cathode materials for Li-ion batteries
Communication

Human serum albumin mutants complexed Mn(III) protoporphyrin IX as superoxide dismutase mimics

Genetically engineered human serum albumin mutants complexed Mn(III) protoporphyrin IX in the haem pocket (subdomain IB) showed superoxide dismutase activity.

Graphical abstract: Human serum albumin mutants complexed Mn(iii) protoporphyrin IX as superoxide dismutase mimics
Communication

Assembled structures of dipyrrins and their oligomers bridged by dioxy-boron moieties

A linear arrangement of BODIPY dimers and trimers was transformed into boron-bridged box, ladder and cage structures on treatment with spacer units possessing multiple diol moieties.

Graphical abstract: Assembled structures of dipyrrins and their oligomers bridged by dioxy-boron moieties
Communication

Synthesis of a hetero-dinuclear metal complex in a porphyrin/phthalocyanine four-fold rotaxane

A hetero-dinuclear metal complex consisted of cofacially stacked Cu2+–porphyrin and Zn2+–phthalocyanine connected by four rotaxanes.

Graphical abstract: Synthesis of a hetero-dinuclear metal complex in a porphyrin/phthalocyanine four-fold rotaxane
Communication

A bis(terpyridine)iron network polymer on carbon for a potential energy storage material

A bis(terpyridine)iron network polymer modified glassy carbon electrode possessing superior electrochemical properties has high potential for energy storage applications.

Graphical abstract: A bis(terpyridine)iron network polymer on carbon for a potential energy storage material
Communication

Programmed crystallization via epitaxial growth and ligand replacement towards hybridizing porous coordination polymer crystals

Hybridized porous coordination polymers with sandwich or core–shell configuration are synthesized either through epitaxial growth or ligand replacement, respectively.

Graphical abstract: Programmed crystallization via epitaxial growth and ligand replacement towards hybridizing porous coordination polymer crystals
Communication

A nanospherical polymer as an MRI sensor without paramagnetic or superparamagnetic species

A pH-responsive nanospherical polymer works as a metal-free magnetic resonance imaging sensor for pH.

Graphical abstract: A nanospherical polymer as an MRI sensor without paramagnetic or superparamagnetic species
Paper

Amphiphilic ferrocenylated alkylpyridinium: the formation of micelles and hydrogels and their disaggregation induced by an external stimulus

Ferrocene-containing amphiphiles [py-N-(CH2)nOCH2Fc]Cl (n = 6, 8, 10; py = C5H5N, Fc = Fe(C5H4)(C5H5)) in aqueous media form micelles which are changed to a solution, pseudorotaxanes with α-cyclodextrin, and their hydrogels upon an outer stimulus.

Graphical abstract: Amphiphilic ferrocenylated alkylpyridinium: the formation of micelles and hydrogels and their disaggregation induced by an external stimulus
Paper

Triple-stranded ferric helices: a π–π interaction-driven structural hierarchy of Fe5, Fe7, and Fe17 clusters

Polypyridyl ligands were used to support triple-stranded helical [Fe5], [Fe7] and [Fe17] complexes. The redox-active complexes were stabilized by increasing degrees of π–π stacking between the ligand moieties.

Graphical abstract: Triple-stranded ferric helices: a π–π interaction-driven structural hierarchy of Fe5, Fe7, and Fe17 clusters
Paper

Trilayer-cubic core–shell structure of PbS/EuS nanocrystals revealed by the combination of the synchrotron small-angle X-ray scattering method and energy-dispersive X-ray spectroscopy

Detailed information on a PbS/EuS/Eu2O3 hetero-nanostructure was obtained by combining SAXS and EDS-TEM data analyses.

Graphical abstract: Trilayer-cubic core–shell structure of PbS/EuS nanocrystals revealed by the combination of the synchrotron small-angle X-ray scattering method and energy-dispersive X-ray spectroscopy
Paper

Highly selective sorption and unique packing geometries of unsaturated hydrocarbons and CO2 in a fluorine-substituted organic–inorganic ionic crystal

Highly selective sorption and unique packing geometries of acetylene and CO2 were observed in a fluorine-substituted organic–inorganic ionic crystal.

Graphical abstract: Highly selective sorption and unique packing geometries of unsaturated hydrocarbons and CO2 in a fluorine-substituted organic–inorganic ionic crystal
Paper

A redox-active porous coordination network film based on a Ru complex as a building block on an ITO electrode

The permselectivity of a porous coordination network film containing a novel Ru complex with 2,6-bis(N-pyridylbenzimidazolyl)-pyridine ligands as a building block was studied by cyclic voltammetry and EQCM measurements.

Graphical abstract: A redox-active porous coordination network film based on a Ru complex as a building block on an ITO electrode
Paper

Theoretical studies of electronic structures, magnetic properties and electron conductivities of one-dimensional Nin (n = 3, 5, 7) complexes

Electronic structures, magnetic properties and electron conductivities of one-dimensional Ni complexes were investigated by DFT calculations.

Graphical abstract: Theoretical studies of electronic structures, magnetic properties and electron conductivities of one-dimensional Nin (n = 3, 5, 7) complexes
Paper

Phosphorescent properties of metal-free diphosphine ligands and effects of copper binding

We studied the luminescence properties of copper(I) complexes containing bis[2-(diphenylphosphino)phenyl]ether (DPEphos), [Cu(DPEphos)(CH3CN)]PF6 (1), [Cu(DPEphos)2]PF6 (2), and copper(I) complexes with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), [Cu(xantphos)(CH3CN)2]PF6 (3), [Cu(xantphos)2]PF6 (4) in the solid state.

Graphical abstract: Phosphorescent properties of metal-free diphosphine ligands and effects of copper binding
Paper

Hydrothermal synthesis of inorganic–organic hybrid gadolinium hydroxide nanoclusters with controlled size and morphology

Inorganic–organic hybrid Gd(OH)3 nanoclusters were synthesized by using 3,4-dihydroxyhydrocinnamic acid (DHCA) which are composed of small nanoparticles interlinked by DHCA molecules and show paramagnetic behavior.

Graphical abstract: Hydrothermal synthesis of inorganic–organic hybrid gadolinium hydroxide nanoclusters with controlled size and morphology
Paper

A distorted honeycomb motif in divalent transition metal compounds based on 4-phosphonbenzoic acid and exchange coupled Co(II) and Cu(II): synthesis, structural description and magnetic properties

The first divalent open shell cobalt phosphonate compound based on a honeycomb motif is presented. The magnetic properties are reported together with those of the corresponding copper compound.

Graphical abstract: A distorted honeycomb motif in divalent transition metal compounds based on 4-phosphonbenzoic acid and exchange coupled Co(ii) and Cu(ii): synthesis, structural description and magnetic properties
Paper

Synthesis and nanostructures of several tetrathiafulvalene derivatives having the side chains composed of chiral and hydrogen-bonding groups and their charge-transfer complexes

Tetrathiafulvalene (TTF) derivatives TTF-Bor, TTF-2UM and TTF-4UM having chiral urethane groups were prepared.

Graphical abstract: Synthesis and nanostructures of several tetrathiafulvalene derivatives having the side chains composed of chiral and hydrogen-bonding groups and their charge-transfer complexes
Paper

Zinc-porphyrins functionalized with redox-active metal peripherals: enhancement of dπ–pπ interaction leading to unique assembly and redox-triggered remote switching of fluorescence

Coupling of the redox-active Fe and Ru fragments with the Zn-porphyrin leads to the unique systems such as redox-triggered switching of fluorescence and supramolecular interaction with guest molecules.

Graphical abstract: Zinc-porphyrins functionalized with redox-active metal peripherals: enhancement of dπ–pπ interaction leading to unique assembly and redox-triggered remote switching of fluorescence
Paper

Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(I) complexes: structures and spectroelectrochemical behaviour

Twofold and fourfold bridging 1,2,4,5-tetracyanobenzene has been observed as an innocent but reducible ligand in complexes with 1,1′-bis(diorganylphosphino)ferrocene-copper(I).

Graphical abstract: Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: structures and spectroelectrochemical behaviour
Paper

Discrete and polymeric heteronuclear constructs derived from triangular 2,2′-bipyrazine complexes of cis-a2PtII (with a = NH3 or a2 = en)

Triangular, vase-shaped PtII complexes of 2,2′-bipyrazine are stitched together in multiple ways by heterometal ions (Cu2+, Cd2+, Ag+). Anion hosting properties of these constructs are pronounced.

Graphical abstract: Discrete and polymeric heteronuclear constructs derived from triangular 2,2′-bipyrazine complexes of cis-a2PtII (with a = NH3 or a2 = en)
Paper

Photovoltaic properties of TiO2 loaded with glutathione-protected silver clusters

Size-selected Ag clusters (Ag15, Ag25 and Ag29) loaded on TiO2 electrodes function as photosensitizers. Ag15 clusters yielded the internal quantum efficiency of 28% at 460 nm in the presence of [Co(bpy)3]2+.

Graphical abstract: Photovoltaic properties of TiO2 loaded with glutathione-protected silver clusters
Open Access Paper

Cathodic photocurrent generation from zinc-substituted cytochrome b562 assemblies immobilized on an apocytochrome b562-modified gold electrode

Hierarchical assemblies of photoactive cytochrome b562 reconstituted with zinc protoporphyrin IX covalently linked with the protein surface were constructed on a gold electrode modified with an apoprotein of cytochrome b562.

Graphical abstract: Cathodic photocurrent generation from zinc-substituted cytochrome b562 assemblies immobilized on an apocytochrome b562-modified gold electrode
Paper

Molecular rectangles from platinum(II) and bridging dicarbene, diisocyanide and 4,4′-bipyridine ligands

The tetranuclear molecular rectangle [18](BF4)8 featuring two different types of bridging di-NHC ligands has been obtained from a dinuclear dicarbene-bridged platinum(II) complex and β,β′-dihydroxyphenyl-1,4-diisocyanide followed by cleavage of the Si–O bonds of the isocyanide.

Graphical abstract: Molecular rectangles from platinum(ii) and bridging dicarbene, diisocyanide and 4,4′-bipyridine ligands
Paper

Adsorption and detection of Escherichia coli using an Au substrate modified with a catecholate-type artificial siderophore–Fe3+ complex

A self-assembled monolayer of a catecholate-type artificial siderophore-Fe3+ complex was prepared and its adsorption and detection abilities for Escherichia coli was investigated.

Graphical abstract: Adsorption and detection of Escherichia coli using an Au substrate modified with a catecholate-type artificial siderophore–Fe3+ complex
Paper

Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells

An oxovanadium(IV/V) couple gave rise to an efficient redox mediation in a DSSC to achieve photovoltaic conversion efficiency exceeding 5%.

Graphical abstract: Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells
Paper

Oxidant-induced intramolecular triazole formation

Coordination of Eu(III)- or Gd(III)-ions by C3-symmetric triaminoguanidinium based ligands leads to 1,2,4-triazole formation. Using Pd(II)-complexes as a model system, this triazole formation could be analyzed in detail using O2 or H2O2 as an oxidation reagent. The steric demand of the PR3-coligand seems to play a key role in the cyclization reaction.

Graphical abstract: Oxidant-induced intramolecular triazole formation
Paper

6-Substituted purines containing thienyl or furyl substituents as artificial nucleobases for metal-mediated base pairing

Purine derivatives with a furyl or thienyl substituent have been investigated in terms of their applicability in metal-mediated base pairs.

Graphical abstract: 6-Substituted purines containing thienyl or furyl substituents as artificial nucleobases for metal-mediated base pairing
Paper

Structure-distortion-induced photomagnetic effect in azobenzene/polyoxometalate Langmuir–Blodgett films

Reversible photoisomerization of azobenzene (AZ) led to a structure-distortion of a polyoxometalate (POM), resulting in the photomagnetic effect.

Graphical abstract: Structure-distortion-induced photomagnetic effect in azobenzene/polyoxometalate Langmuir–Blodgett films
Paper

Metal array fabrication based on ultrasound-induced self-assembly of metalated dipeptides

Pd- and Pt-bound bis-metalated peptides were synthesised by the condensation of Pd- or Pt-aldimine-complex-bound glutamic acids to afford the four possible metal isomers of bis-Pd and bis-Pt-homometalated dipeptides and PdPt- and PtPd-heterometalated dipeptides without metal disproportionation.

Graphical abstract: Metal array fabrication based on ultrasound-induced self-assembly of metalated dipeptides
Paper

Fluorescent colour modulation in Zn(II)-based metallo-supramolecular polymer films by electronic-state control of the ligand

Zn(II)-based metallo-supramolecular polymers showed different luminescent colours of blue, cyan, and green in the film state by ligand modification.

Graphical abstract: Fluorescent colour modulation in Zn(ii)-based metallo-supramolecular polymer films by electronic-state control of the ligand
Paper

Proton-exchange mechanism of specific Cs+ adsorption via lattice defect sites of Prussian blue filled with coordination and crystallization water molecules

Cs+ is trapped by chemical adsorption via the hydrophilic lattice defect sites through proton-elimination.

Graphical abstract: Proton-exchange mechanism of specific Cs+ adsorption via lattice defect sites of Prussian blue filled with coordination and crystallization water molecules
Paper

Programmed multiple complexation for the creation of helical structures from acyclic phenolbipyridine oligomer ligands

Phenol–bipyridine oligomer ligands were designed and synthesized so that the complexation with multiple metal ions leads to single helical complexes in a pre-programmed fashion.

Graphical abstract: Programmed multiple complexation for the creation of helical structures from acyclic phenol–bipyridine oligomer ligands
Paper

Photonic gratings of the metal–organic framework {Fe(bpac)[Pt(CN)4]} with synergetic spin transition and host–guest properties

Optical diffraction, surface plasmon resonance spectroscopy and Raman micro-spectroscopy studies on surface-relief photonic gratings of {Fe(bpac)[Pt(CN)4]}.

Graphical abstract: Photonic gratings of the metal–organic framework {Fe(bpac)[Pt(CN)4]} with synergetic spin transition and host–guest properties
Paper

Programmed functionalization of SURMOFs via liquid phase heteroepitaxial growth and post-synthetic modification

This successful integration of two spatially separated MOFs into one heterostructured film resulted in size selectivity and high storage capacity.

Graphical abstract: Programmed functionalization of SURMOFs via liquid phase heteroepitaxial growth and post-synthetic modification
Paper

Metallo-regulation of the bimolecular triplex formation of a peptide nucleic acid

PNA conjugates incorporating a bipyridine unit were prepared. The conjugate may be useful as an allosteric DNA carrier that releases the DNA in response to a certain metal ion concentration.

Graphical abstract: Metallo-regulation of the bimolecular triplex formation of a peptide nucleic acid
Paper

Self-association and columnar liquid crystalline phase of cationic alkyl-substituted-bipyridine benzenedithiolato gold(III) complexes

The introduction of a Au(III) ion into the asymmetric mesogenic core leads to the formation of self-associating, cationic columnar structures in both the crystalline and rectangular columnar liquid crystalline state.

Graphical abstract: Self-association and columnar liquid crystalline phase of cationic alkyl-substituted-bipyridine benzenedithiolato gold(iii) complexes
Open Access Paper

Plasmon-induced oxidation of gold nanoparticles on TiO2 in the presence of ligands

Au nanoparticles are oxidized by plasmon-induced charge separation in the presence of SCN, Br or Cl, chiefly via direct oxidation. The photopotential of Au is suggested to depend on both the flatband potential of TiO2 and the excitation wavelength.

Graphical abstract: Plasmon-induced oxidation of gold nanoparticles on TiO2 in the presence of ligands
Paper

A liquid-crystalline perylene tetracarboxylic bisimide derivative bearing a triethylene oxide chain and complexation of the derivative with Li cations

Electron- and ion-transporting liquid-crystalline perylene tetracarboxylic bisimide was synthesized. This compound exhibits a lamellar mesophase and electron mobility exceeding 10−3 cm2 V−1 s−1 at room temperature.

Graphical abstract: A liquid-crystalline perylene tetracarboxylic bisimide derivative bearing a triethylene oxide chain and complexation of the derivative with Li cations
Paper

Flexible, linear, tetranuclear palladium complexes supported by tetraphosphine ligands with electron-withdrawing groups

Linear tetranuclear palladium complexes were synthesized by using a new tetraphosphine with electron-withdrawing substituent groups.

Graphical abstract: Flexible, linear, tetranuclear palladium complexes supported by tetraphosphine ligands with electron-withdrawing groups
Paper

Programming MOFs for water sorption: amino-functionalized MIL-125 and UiO-66 for heat transformation and heat storage applications

Reversible water adsorption/desorption renders hydrophilic Ti- and Zr-MOFs interesting candidates for sorption-based chilling or heat pump systems.

Graphical abstract: Programming MOFs for water sorption: amino-functionalized MIL-125 and UiO-66 for heat transformation and heat storage applications
Frontier

Metal complexes in molecular junctions

The use of metal complexes to achieve a conductive molecular junction with a special focus on organometallics is overviewed and illustrated with representative examples. The prospects offered by such compounds owing to their specific properties are discussed.

Graphical abstract: Metal complexes in molecular junctions
58 articles

About this collection

Guest edited by Professors Hiroshi Nishihara and Hiroki Oshio, this themed issue highlights how coordination programming—the molecular design of coordination compounds—is essential for the construction of systems with targeted physical and chemical functionalities.

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