Themed collection 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”.

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.

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

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

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

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

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

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

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

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.

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.

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

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

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

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.

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

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.

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

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

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

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

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.

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.

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

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

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.

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

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.

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.

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.

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

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.

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).

Triangular, vase-shaped Pt^II 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.

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⁺.

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.

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.

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.

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

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.

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

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

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.

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

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

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.

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

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

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.

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.

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.

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.

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

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

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.