Coordination Programming: A New Concept for the Creation of Multifunctional Molecular Systems

Nishihara, Hiroshi

doi:10.1246/cl.140010

Chemistry Letters

2014

DOI: 10.1246/cl.140010

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Coordination Programming: A New Concept for the Creation of Multifunctional Molecular Systems

Hiroshi Nishihara

Abstract: Hill (19871989) and as a researcher of PRESTO, JRDC (19921996). His research has been focused on creation of new electro-and photofunctional materials comprising both transition metals and π-conjugated chains and invention of unidirectional electron-transfer systems utilizing molecular layer interfaces.

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Cited by 78 publications

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“…1 For example, helical metal complexes of π-conjugated molecules are potential molecular systems that exhibit attractive chiral electronic and optical properties, 2 asymmetric catalytic properties, 3 and macromolecular chiral amplification. 4 Considering the geometries of π-conjugated systems, linear metalcoordination ligand molecules, in contrast with planar molecules such as porphyrins, seem preferable for the fabrication of such helical structures with fascinating chiral properties.…”

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confidence: 99%

Helical π-Systems of Bidipyrrin–Metal Complexes

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Various metal-bridged single and double helical complexes of π-conjugated ligand molecules, bidipyrrins, were prepared. The introduction of terminal end units enabled the formation of chiral single and double helices; their spectroscopic properties and temperature-dependent behaviors were examined.Coordination programming is a new concept for the fabrication of a variety of metal complexes with potential application as functional materials and in devices.1 For example, helical metal complexes of π-conjugated molecules are potential molecular systems that exhibit attractive chiral electronic and optical properties, 2 asymmetric catalytic properties, 3 and macromolecular chiral amplification. 4 Considering the geometries of π-conjugated systems, linear metalcoordination ligand molecules, in contrast with planar molecules such as porphyrins, seem preferable for the fabrication of such helical structures with fascinating chiral properties.5 As a candidate for linear building subunits involved in helical π-conjugated systems, bidipyrrin (1, Figure 1), which is a directly linked linear tetrapyrrolic dipyrrin dimer, 6 can form various complexing modes according to the metal cations involved: bidipyrrins form [1 + 1]-type fairly planar complexes with cations such as Ni II and Cu II , 7 whereas they provide [2 + 2]-type double helical complexes with cations such as Zn II . 8,9 Therefore, the introduction of appropriate terminal end units to bidipyrrins would enable the formation of helical metal complexes in various modes.α-Phenyl-substituted bidipyrrin 2 (Figure 1) was prepared in 16% yield through the acid-catalyzed condensation of 5,5¤-bis(hydroxyphenylmethyl)bipyrrole 10 and 2-phenylpyrrole and subsequent oxidation by p-chloranil. The synthetic procedure differs from that for 1, for which intramolecular oxidation coupling of the corresponding dipyrrinNi II complex and subsequent demetallation were conducted. The UVvis absorption maxima ( max ) of 2 in CHCl 3 were observed at 455 and 667 nm, which were red-shifted relative to those of 1 at 412 and 587 nm.

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Helical π-Systems of Bidipyrrin–Metal Complexes

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“…Therefore, a new method to spatially "program" coordination reactions 8 is a prerequisite for structuring PCPs in a desired dimension.…”

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Fibrous Architectures of Porous Coordination Polymers–Alumina Composites Fabricated by Coordination Replication

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Polycrystalline fibers of porous coordination polymers (PCPs) were synthesized from free-standing alumina nanofiber materials by a coordination replication process. The diameter and morphology of fibrous PCP architectures were controlled by the concentration of aluminum salts and the pH of the reaction solution of replication, respectively. CO 2 adsorption measurement proved the presence of hierarchical porosity composed of both micropores and mesopores in PCP fibers.Porous coordination polymers (PCPs) or metalorganic frameworks (MOFs), crystalline coordination frameworks with an intrinsic microporosity, are an intriguing class of porous materials for applications in storage and separation of molecules. 1 The improvement of porous properties has relied on the modification of pore surface by introducing chemical functionality or on the control of pore size and shape by replacing linkers with the same geometry.2 Apart from these molecular-scale modifications, structuring of PCPs on a mesoscopic or macroscopic scale, in which PCP nanocrystals as building blocks are assembled into higher-order architectures, has very recently emerged as an orthogonal approach to molecular modification for the improvement of material performance.3 Using template approaches or microfabrication technologies, it was found that assemblages of PCP crystals, for instance, zero-dimensional (0D) hollow spheres, 4 two-dimensional (2D) patterns, 5 or threedimensionally (3D) extended architectures 6 demonstrated characteristic properties depending on material morphologies. 3Among higher-order architectures, one-dimensional (1D) nanofiber morphology remains largely unexplored, except for a very limited number of reports.7 This is simply because of the limitation of the fabrication protocol; PCPs are constructed via an assembly of metal ions and organic links so that the confinement of the coordination reaction into one dimension is quite challenging. Therefore, a new method to spatially "program" coordination reactions 8 is a prerequisite for structuring PCPs in a desired dimension.In this study, we synthesized 1D fibrous macroscopic architectures of PCP crystals by the direct conversion of alumina to aluminum-based PCPs while maintaining macroscopic fibrous morphology. We recently proposed this method, so-called "coordination replication," 9 for the fabrication of 2D honeycomb patterns, 3D extended architectures, 9 or hybrid gold nanorods PCP coreshell composites. 10 In this manuscript, we describe the conversion of 1D alumina nanofibers to aluminum-based PCP nanofibers, [Al(OH)(L)] n (L = 1,4-naphthalanedicarboxylate (ndc) or 1,4-benzenedicarboxylate (bdc)), as shown in Figure 1.This strategy relies on the use of sacrificial metal oxides both as a solid-state metal source and structure-directing agents. Since metal oxides can easily be shaped into desired architectures using a solgel process or the thermal oxidation of corresponding metal salts, these methods offer powerful means to produce various designed PCP-based structures. Here, electro...

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“…2,3 We have synthesized 2D MOF nanosheets (NAFS) by a bottom-up approach utilizing reactions at the airliquid interface.…”

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Porphyrin-based Coordination Polymer Composed of Layered Pillarless Two-dimensional Networks

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Single crystals of a layer-structured coordination polymer, BNAS-11 [ZnTCPP(H 2 O)Zn 2 (H 2 O) 2 ] (ZnTCPP: 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinatozinc(II)), were obtained. Tetratopic ZnTCPP molecules are connected through dimer zinc paddle-wheel secondary building units and form a two-dimensional (2D) network with square grids. The layers are stacked electrostatically without the need of binding pillar ligands.Two-dimensional (2D) nanomaterials with monomolecular thickness are of considerable interest because they exhibit unique properties due to their dimensionality and can be utilized as extremely small components in nanodevices.1 Coordination compounds, including metalorganic frameworks (MOFs) or porous coordination polymers (PCPs), are attractive for assembling 2D nanosheets as their structures can be rationally designed from inorganic and organic building units and are endowed with various functionalities.2,3 We have synthesized 2D MOF nanosheets (NAFS) by a bottom-up approach utilizing reactions at the airliquid interface.4 Molecular building units with peripheral coordinative parts are spread on the surface of an aqueous solution of metal-ion linkers. This initiates a coordinative reaction at the interface and results in the formation of 2D MOF nanosheets. 4 The synthetic protocol is not restricted to MOFs and can be used for the creation of various 2D coordination compounds 5 as the reactants are strictly restricted to the direction parallel to the surface. Another way to obtain 2D nanosheets of various materials (e.g., graphite, 1c metal oxides, 1d transitionmetal chalcogenides, 1e and organic polymers 1f ) is by exfoliating the bulk crystals with layered structures; the starting components are strongly connected laterally, while the 2D layers are weakly stacked, allowing peeling by physical and chemical treatments.(Metallo)porphyrins are stable macrocyclic ligands with square-planar geometry 3c,3d,6 and are excellent candidates for constructing 2D nanonetworks through a suitable choice of peripheral coordinative substituents and metal-ion linkers. However, it is difficult to exfoliate MOF crystals as removal of the counter ions needed for charge balance destabilizes the peeled layers 3e3g or the individual layers are rigidly connected vertically by bidentate pillars.3h,3i On the other hand, porphyrinbased MOF crystalline materials without any pillars, reminiscent of the interlayer stacking mode of the NAFS nanofilms, 4 grown by the LangmuirBlodgett layer-by-layer (LB-LbL) methodology are rare. 3j,3kHere we report the isolation of a new bulk analogue of crystalline NAFS thin films [ZnTCPP(H 2 O)Zn 2 (H 2 O) 2 ] (designated BNAS-11). It is a polymorph of the PPF-1 MOF, 3k retaining the same ZnTCPPZn sheet structure but adopting a different stacking sequence perpendicular to the layers. The existence of such multiple polymorphs with differing sheet stacking patterns reflects the weak interlayer interactions and provides opportunities for facile exfoliation of the crystals to obtain 2D nanosh...

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Coordination Programming: A New Concept for the Creation of Multifunctional Molecular Systems

Cited by 78 publications

References 48 publications

Helical π-Systems of Bidipyrrin–Metal Complexes

Helical π-Systems of Bidipyrrin–Metal Complexes

Fibrous Architectures of Porous Coordination Polymers–Alumina Composites Fabricated by Coordination Replication

Porphyrin-based Coordination Polymer Composed of Layered Pillarless Two-dimensional Networks

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