Stepwise construction of grid-type Cu(ii)–Cd(ii) heterometallic MOFs based on an imidazole-appended dipyrrin ligand

Béziau, Antoine; Baudron, Stéphane A.; Pogozhev, Dmitry; Fluck, Audrey; Hosseini, Mir Wais

doi:10.1039/c2cc35543d

Cited by 41 publications

(21 citation statements)

References 43 publications

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“…[80][81][82][83][84][85][86][87] They utilized heterometallic bis(dipyrrinato)metal complex networks using dipyrrin ligands with pyridine or benzonitrile at the meso-position. These peripheral N-bearing moieties may be utilized as additional coordination sites for silver(I) [80][81][82] and cadmium(II) 83,84 centers to form heterometallic coordination polymers. Moreover, silver(I) ions may experience silver(I)-π interactions, which also contribute to network formation.…”

Section: Metal-organic Framework and Porous Coordination Polymersmentioning

confidence: 99%

New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications

et al. 2015

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Dipyrrins serve as monovalent bidentate ligand molecules that coordinate to various cations. Their BF 2 complexes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene and its derivatives (BODIPYs), exhibit excellent photostability, strong light absorption, and high fluorescence quantum yield, thereby encouraging their application in various fields, e.g., as biological and biomedical fluorescent markers. Dipyrrin may also accept a wide variety of metal ions spontaneously. However, dipyrrin metal complexes have been disregarded from materials science research. This review article summarizes recent progress in bis(dipyrrinato)metal(II) and tris(dipyrrinato)metal(III) complexes from the viewpoint of materials chemistry. Section 2 describes a series of efforts aimed to realize intense luminescence superior to or comparable with that of BODIPYs. The spontaneous coordination of these complexes enables them to construct self-assembled nanoarchitectures, such as supramolecules and coordination polymers that form one-dimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks. Section 3 describes such alluring molecular superstructures. Section 4 discusses potential applications based on these nanoarchitectures, such as thermoelectric and photoelectric conversion. aimed to realize intense luminescence superior to or comparable with that of BODIPYs. Section 3 discusses the selfassembly of bis and tris(dipyrrinato)metal complexes, which results in the formation of alluring nanoarchitectures, such as supramolecules and coordination polymers giving rise to onedimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks (MOFs) and porous coordination polymers (PCPs). Section 4 describes potential applications based on these nanoarchitectures. Pursuit of bright luminescenceA plain BODIPY shows intense absorption and bright fluorescence at approximately 500 nm, which are derived from the 1 π-π * transition of the dipyrrinato ligand. 5-16 The absorption and fluorescence may be redshifted upon the introduction of substituents on the dipyrrinato ligand, covering the region 500-900 nm. BODIPYs are good fluorophores even in polar solvents such as water. In sharp contrast, dipyrrin metal complexes have long been believed to be non-luminescent or weakly luminescent. This drawback seriously reduces the value of dipyrrinato-metal complexes in applications in which they serve, for example, as photosensitizers. In this section, the authors concentrate on efforts to improve the luminescent ability of bis and tris(bisdipyrrinato)metal complexes. For comprehensive knowledge on the whole types of luminescent dipyrrinato-metal complexes (i.e. mono(dipyrrinato)metal complexes with ancillary ligands other than dipyrrins), please see a comprehensive review article contributed by Baudron. 2

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Section: Metal-organic Framework and Porous Coordination Polymersmentioning

confidence: 99%

New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications

et al. 2015

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“…Single-crystal structural analysis shows that there are one crystallographically independent cadmium ion, two zinc ions, two mip 2-dianions, two Hmip -anions, and one neutral bpe molecule in the asymmetric unit of complex 1 (see Figure 1) -, and to two deprotonated carboxylic oxygen atoms of two mip 2-. However, the Zn1-O8A distance suggests a non-negligible interaction, the coordination sphere around the Zn II atom should be reasonably described as a seriously distorted 4+1 square pyramidal arrangement {ZnNO 4 }with τ = 0.398. [9] Remarkably, the H 2 mip dicarboxylic acids show different degrees of deprotonation, where the deprotonated mip 2- It is noteworthy that each {CaO 6 } polyhedron shares four corners with the adjacent four identical {CaO 6 } polyhedra, extending into an undulating 2D layer constructing from mip 2-dianions in the (001) plane (see Figure 2).…”

Section: Resultsmentioning

confidence: 99%

“…[3] The heterometallic MOFs based on at least two different metal cations seem more synthetically challenging and the number of related publications is still limited. [4] As an interesting class of organic-inorganic hybrid materials, the heterometallic nature provides multiplicity in topological structures and physical properties. Regarding heterometallic frameworks, synthetic strategy using mixed 3d-3d, 3d-4f, 3d-3d-4f metals with distinct electron configurations, has been developed to construct MOFs with versatile organic ligands.…”

Section: Introductionmentioning

confidence: 99%

A Distorted pcu Topological Heterometallic Metal‐Organic Framework with Right‐ and Left Chiral Covalent Layers

Wen

Han

Wang

et al. 2013

Zeitschrift anorg allge chemie

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Abstract.An unusual heterometallic 3D framework, [Zn 2 Ca(mip) 2 (Hmip) 2 (bpe)] n (1), was synthesized by using an alkaliearth metal (calcium) and a d 10 metal (zinc) under hydrothermal conditions [H 2 mip = 5-methylisophthalic acid, bpe = 1,2-bi(4-pyridyl)ethene]. Single-crystal X-ray analysis shows that complex 1 is a pillaredgrid metal-organic framework (MOF) with nanosized parallelogram channels fully occupied by dangling Hmip -pendants. The most fasci-

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“…From a large subset of bimetallic complexes, heterobimetallic complexes and their chemistry has been developed with the idea of exploiting synergistic effects between the two metal centers [11]. To data, despite intensive studies on the photochemistry and photo-physics of heterobimetallic d 8 -d 8 and d l0 -d l0 complexes [12][13][14][15], corresponding research on the heterobimetallic d 10 -d 8 system is still sparse [16][17][18][19]. We report here the synthesis, crystal structure, and luminescent property of one new microporous heterometallic complex of Cd(II) and Cu(II) [Cd 2 Cu(BTC) 2 (H 2 O) 2 ]Á2H 2 O (1) (BTC = benzene-1,3,5-tricarboxylate).…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structure and luminescent property of heterometallic d10–d8 porous complex

Zhang

Wang

Chen

2015

Journal of Molecular Structure

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Stepwise construction of grid-type Cu(ii)–Cd(ii) heterometallic MOFs based on an imidazole-appended dipyrrin ligand

Abstract: An imidazole-appended dipyrrin ligand yields, upon coordination to Cu(II) cations, a linear metallatecton that self-assembles with Cd(II) salts to afford 2D grid-type MOFs which, upon parallel stacking, lead to porous crystals offering 1D channels.

Cited by 41 publications

References 43 publications

New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications

New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications

A Distorted pcu Topological Heterometallic Metal‐Organic Framework with Right‐ and Left Chiral Covalent Layers

Synthesis, crystal structure and luminescent property of heterometallic d10–d8 porous complex

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