Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

Drath, Olga; Boskovic, Colette

doi:10.1016/j.ccr.2017.11.025

Cited by 93 publications

(73 citation statements)

References 73 publications

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“…[3,4] Cobalt is a promising alternative to platinum and ruthenium due to its abundance and therefore lower cost, reduced toxicity (it is an essential trace element) and two oxidation states accessible under biological conditions -an inert Co 3+ (low spin 3d 6 ) and a labile Co 2+ (high spin 3d 7 ) configuration. [6,7] Some of these features allow a wide range of potential applications not only in medicinal chemistry, [4,6,7] but also in the development of molecular materials [8,9] and catalysts for water splitting and CO 2 reduction, [10][11][12] among others. Differently from platinum and ruthenium, the metal is not responsible for the activity of cobalt prodrugs.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Cobalt(III)‐Tetrachlorocatechol Complexes as Models for Catechol‐Based Anticancer Prodrugs

et al. 2019

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Two novel cobalt(III) complexes, [Co(TPA)(TCC)]ClO4·H2O (1) and [Co(py2en)(TCC)]ClO4·2H2O (2), were synthesized and fully characterized by IR, UV/Vis and 1H NMR spectroscopy, ESI mass spectrometry, and X‐ray diffraction. Cyclic voltammetry experiments revealed an irreversible reduction of the Co3+ center for both complexes. The Co3+/Co2+ redox potential, –0.91 V for 1 and –1.15 V for 2 (vs. Fc/Fc+), was obtained by square wave voltammetry in DMSO. Reactions of 1 and 2 with ascorbic acid and sodium dithionite at pH 7.4 and 6.2 were carried out in argon and open‐air atmospheres, to simulate biological redox activation under hypoxia and normoxia. Neither the Co3+/Co2+ reduction nor the dissociation of TCC2– was observed. Thermodynamic parameters calculated for the Co3+/Co2+ reduction and substitution of the TCC2– ligand by water indicate an endothermic non‐spontaneous reaction.

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Section: Introductionmentioning

confidence: 99%

Investigation of Cobalt(III)‐Tetrachlorocatechol Complexes as Models for Catechol‐Based Anticancer Prodrugs

et al. 2019

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“…Progress in supramolecular chemistry has led to switchable molecules capturing widespread attention. Although the denotation of “switching” has been variably employed in the literature, for the purposes of limiting the scope of this Review the term “switch” will signify any system that, upon exposure to a particular, external stimulus, such as light, temperature, or electrical field, undergoes a reversible and controllable transformation between two or more distinct molecular states, commonly involving isomerization, bond breaking or formation, the gain or loss of electrons, or conformational changes. Under ideal conditions, it is assumed that every stage in the transformation of a reversible process is in equilibrium with the next state and the prior state, so that infinitesimally small reversal steps along the reaction coordinate will yield a state indistinguishable to that from before the process began.…”

Section: Introductionmentioning

confidence: 99%

Switching in Metal–Organic Frameworks

et al. 2019

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In recent years, metal–organic frameworks (MOFs) have become an area of intense research interest because of their adjustable pores and nearly limitless structural diversity deriving from the design of different organic linkers and metal structural building units (SBUs). Among the recent great challenges for scientists include switchable MOFs and their corresponding applications. Switchable MOFs are a type of smart material that undergo distinct, reversible, chemical changes in their structure upon exposure to external stimuli, yielding interesting technological applicability. Although the process of switching shares similarities with flexibility, very limited studies have been devoted specifically to switching, while a fairly large amount of research and a number of Reviews have covered flexibility in MOFs. This Review focuses on the properties and general design of switchable MOFs. The switching activity has been delineated based on the cause of the switching: light, spin crossover (SCO), redox, temperature, and wettability.

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“…Fortschritte in der supramolekularen Chemie führten dazu, dass schaltbare Moleküle eine breite Beachtung erfuhren. Die Bezeichnung “Schalten” wird in der Literatur recht vielfältig verwendet. Daher soll zur Einschränkung des Umfangs dieses Aufsatzes der Begriff “Schalten” hier jedes System bezeichnen, das bei Exposition gegenüber einem bestimmten externen Stimulus, etwa Licht, Temperatur oder ein elektrisches Feld, eine reversible und steuerbare Umwandlung zwischen zwei oder mehr unterschiedlichen molekularen Zuständen erfährt.…”

Section: Introductionunclassified

Schalten in Metall‐organischen Gerüsten

et al. 2019

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Aufgrund ihrer einstellbaren Poren und nahezu grenzenlosen Strukturdiversität, die sich aus dem Design verschiedener organischer Linker und metallischer Strukturbaueinheiten ableitet, haben sich Metall‐organische Gerüste (MOFs) in den vergangenen Jahren zu einem intensiv beforschten Gebiet entwickelt. Zu den größten Aufgaben gehören schaltbare MOFs und ihre Anwendung. Schaltbare MOFs sind “intelligente” Materialien, die bei Exposition gegenüber externen Stimuli eine deutliche, reversible, chemische Veränderung ihrer Struktur durchlaufen, was interessante technische Anwendungen ermöglicht. Obwohl dieser Prozess des Schaltens Ähnlichkeiten mit Flexibilität aufweist, haben sich nur sehr wenige Studien speziell mit Schalten beschäftigt, wohingegen sich eine recht große Zahl von Arbeiten und Übersichten mit der Flexibilität in MOFs beschäftigt. Dieser Aufsatz konzentriert sich auf die Eigenschaften und das allgemeine Design schaltbarer MOFs. Dabei wird die Schaltaktivität basierend auf der Ursache des Schaltens beschrieben: Licht, Spincrossover, Redoxchemie, Temperatur und Benetzbarkeit.

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Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

Cited by 93 publications

References 73 publications

Investigation of Cobalt(III)‐Tetrachlorocatechol Complexes as Models for Catechol‐Based Anticancer Prodrugs

Investigation of Cobalt(III)‐Tetrachlorocatechol Complexes as Models for Catechol‐Based Anticancer Prodrugs

Switching in Metal–Organic Frameworks

Schalten in Metall‐organischen Gerüsten

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