A facile building-block synthesis of multifunctional lanthanide MOFs

Tanase, Stéfania; Mittelmeijer‐Hazeleger, Marjo C.; Rothenberg, Gadi; Mathonière, Corine; Jubera, Véronique; Smits, J.M.; Gelder, René de

doi:10.1039/c1jm12789f

Cited by 44 publications

(42 citation statements)

References 29 publications

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“…The length of the VvO bond (V1-O2 = 1.598(2) Å) is on the lower side compared to the reported values for vanadyl compounds. 24,44 This value and the relatively high VvO stretching frequency (976 cm −1 ) indicates a strong VvO bond. The coordination geometry of the vanadium is distorted octahedral.…”

Section: Resultsmentioning

confidence: 90%

A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate

et al. 2015

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We present a new coordination polymer, {[VO(pzdc)(H2O)2] H2O}n, built from vanadyl and pyrazine-2,5-dicarboxylate (pzdc) ions. It consists of a one-dimensional chain of vanadyl ions linked by pzdc ions. The carboxylate groups show monodentate coordination, while the pyrazine ring is present both in non-coordinated and coordinated modes. This novel structure is stabilized by an intricate network of hydrogen bonds. The material is highly robust, and thermally stable up to 400 K. It is also antiferromagnetic, with a maximum magnetic susceptibility at ca. 50 K. The orbital shape and population analysis by means of DFT analysis confirm the π-acceptor role of the aromatic nitrogen function of the ligand, while the oxygen-based moieties (carboxylates from pzdc, the aqua ligands and oxo from V=O group) behave as normal donors. Charting the density flow related with significant transitions computed by time-dependent DFT, we determined the ligand-to-metal charge transfer processes. The topology of the chain complex implies two different types of connecting bridges. Using Broken Symmetry DFT modelling gives evidence for two different exchange coupling mechanisms between the vanadyl ions along each of these two molecular bridges. One is strongly antiferromagnetic, practically reducing the chain to 'vanadyl dimers'. The other is almost uncoupled, due to the large distance between the vanadyl ions.

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Section: Resultsmentioning

confidence: 90%

A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate

et al. 2015

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“…It enables the observation of visible and NIR photoluminescence of accompanying emissive chromophores [32]. In effect, a considerable number of photoluminescent d–f coordination networks based on octacyanidometallates were reported (Figure 7 and Figure 8, Table 4) [101,102,103,104,105,106,107,108,109,110]. In the aqueous solution, trivalent lanthanide(3+) and [M V (CN) 8 ] 3− ions produce the cyanido-bridged [Ln III (H 2 O) 5 ][M V (CN) 8 ] (Ln = Sm, Eu, Gd, Tb; M = Mo, W) layered frameworks of a square grid topology [101,102,103].…”

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

“…The interesting luminescent functionalites were presented for the three-dimensional hybrid inorganic-organic [Ln III 2 (mpca) 2 (MeOH) 2 (H 2 O) 6 ][Mo IV (CN) 8 ]· x MeOH (Ln = Nd, Eu, Tb; mpca = 5-methyl-2-pyrazine carboxylic acid) networks where cyanido-bridged layers are connected in the third direction by organic mpca linkers [105]. They reveal the strong 4f-metal centred photoluminescence sensitized by mpca ligands while [Mo IV (CN) 8 ] 4− serves as an inorganic linker stabilizing the 3D coordination network.…”

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

2017

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Solid-state functional luminescent materials arouse an enormous scientific interest due to their diverse applications in lighting, display devices, photonics, optical communication, low energy scintillation, optical storage, light conversion, or photovoltaics. Among all types of solid luminophors, the emissive coordination polymers, especially those based on luminescent trivalent lanthanide ions, exhibit a particularly large scope of light-emitting functionalities, fruitfully investigated in the aspects of chemical sensing, display devices, and bioimaging. Here, we present the complete overview of one of the promising families of photoluminescent coordination compounds, that are heterometallic d–f cyanido-bridged networks composed of lanthanide(3+) ions connected through cyanide bridges with polycyanidometallates of d-block metal ions. We are showing that the combination of cationic lanthanide complexes of selected inorganic and organic ligands with anionic homoligand [M(CN)x]n− (x = 2, 4, 6 and 8) or heteroligand [M(L)(CN)4]2− (L = bidentate organic ligand, M = transition metal ions) anions is the efficient route towards the emissive coordination networks revealing important optical properties, including 4f-metal-centred visible and near-infrared emission sensitized through metal-to-metal and/or ligand-to-metal energy transfer processes, and multi-coloured photoluminescence switchable by external stimuli such as excitation wavelength, temperature, or pressure.

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“…Desde então, muitos autores têm utilizado este método, trazendo novas contribuições. Um exemplo é a síntese reportada por Tanase et al 29 de MOFs à base de lantanídeos. Os autores comentam que a grande esfera de coordenação dos lantanídeos faz com que não seja fácil inseri-los em uma estrutura altamente ordenada como as MOFs.…”

Section: Síntese E Modificações Pós-síntese De Mofsunclassified

Redes metalorgânicas e suas aplicações em catálise

Ramos¹,

Tanase²,

Rothenberg³

2014

Quím. Nova

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METAL-ORGANIC FRAMEWORKS AND THEIR APPLICATIONS IN CATALYSIS.Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by choosing the appropriate ligands and metal precursors. Here we review the key aspects of synthesis and characterization of MOFs, focusing on lanthanide-based and vanadium-based materials. We also outline some of their applications in catalysis and materials science.Keywords: carboxylate linker; lanthanide; vanadium. INTRODUÇÃODesde a primeira metade do século XIX, a partir dos estudos de Berzelius, os catalisadores são investigados pela comunidade científi-ca e aplicados em diversos processos industriais. Ao longo da evolução dos estudos da Catálise, a introdução de técnicas de caracterização superficiais, a modelagem molecular e o desenvolvimento de métodos de síntese avançados transformaram a preparação de catalisadores de uma arte à base da tentativa e erro (a partir do conhecimento químico e experiência do pesquisador) em uma ciência multidisciplinar que permite o projeto molecular de catalisadores sólidos específicos para determinada aplicação. Destacam-se o desenvolvimento na síntese de zeólitas, "zeotypes" e materiais mesoporosos, que permitiram a introdução, identificação e otimização de sitos ativos bem definidos (prótons, ácidos de Lewis, redox) na estrutura destes materiais. 1No entanto, as dimensões dos poros das zeólitas e zeotypes limitavam as reações para moléculas com tamanho inferior a 1 nm, até a descoberta de zeólitas com poros maiores, na faixa dos mesoporos. Mesmo assim, algumas reações são limitadas nestes materiais pelo tamanho dos poros incompatíveis com moléculas como triglicerídeos e metaloporfirinas. Além disso, o controle e modulação das propriedades eletrônicas dos sítios ativos da rede ainda é muito limitado em comparação aos catalisadores à base de complexos de metais de transição. Esses problemas foram um pouco contornados com o desenvolvimento de materiais mesoporosos, mas os resultados ainda são limitados.Nesse contexto, surgem os polímeros de coordenação, que combinam as funcionalidades de seletividade de poros e a modulação de propriedades eletrônicas dos organometálicos. Eles podem ser definidos como uma extensa rede de íons ou agrupamentos (clusters) metálicos coordenados a moléculas orgânicas multidentadas, em dimensões porosas bem definidas. As redes metalorgânicas (metal organic frameworks-MOFs) pertencem a uma nova classe de polímeros de coordenação com desenvolvimento bem recente que alia três características: cristalinidade, alta porosidade e existência de forte interação metal-ligante orgânico.2 Na sua síntese pode-se modular tanto a estrutura porosa quanto as propriedades eletrônicas do sítio ativo, escolhendo cuidadosamente o ligante orgânico ou o modificando com tr...

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A facile building-block synthesis of multifunctional lanthanide MOFs

Cited by 44 publications

References 29 publications

A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate

A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

Redes metalorgânicas e suas aplicações em catálise

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