Valence‐Tautomeric Metal–Organic Nanoparticles

Imaz, Inhar; Maspoch, Daniel; Rodríguez-Blanco, Clara; Pérez-Falcón, José Manuel; Campo, Javier; Ruiz‐Molina, Daniel

doi:10.1002/anie.200705263

Cited by 143 publications

(79 citation statements)

References 62 publications

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“…7,26 When the crystal was illuminated, light-induced change in charge distribution occurredknown as ligand-to-metal charge transfer (LMCT)so that the complex unit along the chain direction underwent an elongation of the Co−N bond and thus an anisotropic expansion of the crystal volume. Recently, an interesting VT complex, [Co III (3,5-DBCat)(3,5-DBSq)(bipy)] (bipy = 4,4′-bipyridine), 27 was obtained, which confirmed the strategy of using bridging ligand to achieve functional materials in the nanoparticle-formation process. This complex showed an abrupt VT transition near room temperature.…”

Section: ■ Introductionmentioning

confidence: 73%

Valence Tautomeric Transitions of Three One-Dimensional Cobalt Complexes

et al. 2014

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Three novel complexes, namely, [Co(III)(3,5-DBCat)(3,5-DBSq)(bpe)]·2CH3CN·2H2O (1·S), [Co(III)(3,5-DBCat)(3,5-DBSq)(azpy)]·2CH3CN·2H2O (2·S), and [Co(II)(3,5-DBSq)2(bpb)][Co(III)(3,5-DBCat)(3,5-DBSq)(bpb)]0.5·2CH3CN·2H2O (3·S), were synthesized and characterized by valence tautomeric (VT) X-ray diffraction and magnetic measurements [where 3,5-DBCatH2 = 3,5-di-tert-butyl-catechol, 3,5-DBSqH = 3,5-di-tert-butyl-semiquinone, bpe = trans-bis(4-pyridyl)ethylene, azpy = trans-4,4'-azopyridine, and bpb = 1,4-bis(4-pyridyl)benzene]. The three complexes have similar one-dimensional chain structure building from bidentate-bridging pyridine ligands and planar 3,5-DBCat/3,5-DBSq-fixed Co(II/III) entities. Complexes 1·S and 2·S could retain the crystallinity during desolvation, and the crystal structures of 1 and 2 were therefore able to be determined. Only when 1·S and 2·S desolvated above 310 K did the magnetic susceptibilities × temperatures values of the two complexes rise sharply, and then thermally induced complete, one-step VT transitions for 1 and 2 were available and repeatable. Complex 3·S showed an incomplete, one-step VT transition independent of solvent molecules. Among these complexes, only 1 was sensitive to photoexcitation at low temperature, its photoinduced metastable state relaxed with temperature-independent behavior at low temperature range (5-10 K) and with thermally assisted behavior at high temperature range (above 20 K), respectively.

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Section: ■ Introductionmentioning

confidence: 73%

Valence Tautomeric Transitions of Three One-Dimensional Cobalt Complexes

et al. 2014

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“…Imaz et al [206], reported the synthesis of [Co III (BIX)(3,5-DBSQ)(3,5-DBCAT)] n MOF nano-and microparticles via fast water-assisted precipitation from an ethanolic solution containing Co(OAc) 2 ·4H 2 O, 3,5-di-tert-butyl-1,2-catechol (3,5-DBSQ and 3,5-DBCAT are semiquinonate radical and catecholate forms of 3,5-di-tert-butyl-1,2-benzoquinone, respectively; BIX is 1,4-bis(imidazol-1-ylmethyl)benzene). MOF particle size could be tuned by regulating the rate of water addition (initiation solvent) to the reaction mixture.…”

Section: Initiation Solventmentioning

confidence: 99%

Multi-scale crystal engineering of metal organic frameworks

Seoane

Castellanos

Dikhtiarenko

et al. 2016

Coordination Chemistry Reviews

265

163

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“…[80,81] Alternatively, NMOF particles can be generated by adding a poor solvent to a precursor solution containing MOF reaction components. [82][83][84] However, rational design of structures, in terms of shape, chemical composition and functionality for specific applications, remains a challenge. Here follow a few recent highlights from this area.…”

Section: Metal-organic Framework (Mofs)mentioning

confidence: 99%

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Wang¹,

McHale²

2010

Macromol. Rapid Commun.

113

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The incorporation of metallic units into polymer chains has emerged as a promising route towards functional metal-containing (nano)materials. The resulting polymers possess rich functions derived from their metallic elements, such as redox, optical, catalytic and magnetic properties. In addition, the directional and dynamic nature of metal coordination interactions provides further variables for the exploration of novel materials with designed nanostructures. These types of polymers can be synthesized through direct metal-ligand coordination or chain polymerization of metal containing monomers. Depending on the polymerization techniques and starting components, the resulting polymers, akin to their organic counterparts, can be produced in the form of insoluble networks, processible chain structures, gels or colloids. Research into this rising multidisciplinary subject has benefited from recent progress in several related areas such as supramolecular chemistry, colloidal chemistry etc., with the combination of the relative merits of each ensuring further developments in each individual discipline. For example, as a result of studies into organometallic block copolymers self-assembly behavior, living supramolecular polymerization has been unprecedentedly realized for the architectural design of micelles (see image on the right). Nevertheless, the field is still in a developmental stage and offers ample opportunities for fundamental research, as well as material exploration. In this Feature Article, we intend to overview the field with a brief survey of recent literature.

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Valence‐Tautomeric Metal–Organic Nanoparticles

Cited by 143 publications

References 62 publications

Valence Tautomeric Transitions of Three One-Dimensional Cobalt Complexes

Valence Tautomeric Transitions of Three One-Dimensional Cobalt Complexes

Multi-scale crystal engineering of metal organic frameworks

Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

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