How to get the desired reduction voltage in a single framework! Metallacarborane as an optimal probe for sequential voltage tuning

Tarrés, Màrius; Arderiu, Víctor Sánchez; Zaulet, Adnana; Viñas, Clara; Biani, Fabrizia Fabrizi de; Teixidor, Francesc

doi:10.1039/c5dt01464f

Cited by 27 publications

(27 citation statements)

References 28 publications

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“…Redox potentials of complex 3 corresponding to the Fe and Co centers are 0.06 V higher than that of ferrocene[3e] and 0.22 V lower than that of the cobalt bis(dicarbollide) anion, respectively, indicating electron density movement from the iron center in ferrocene to the cobalt metal in cobalt bis(dicarbollide). The Δ V difference of 1.78 V between Co and Fe metal centers is comparable with the 1.74 V difference when measured individually . The absence of two separate signals for the ferrocene units in complex 3 can be interpreted as the absence of communication between the two end groups.…”

Section: Resultssupporting

confidence: 64%

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

et al. 2018

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The electronic interaction between two terminal ferrocenyl units connected by the cobalt bis(dicarbollide) anion linker was investigated. The bis(ferrocenylethynyl)cobalt bis(dicarbollide) anion (3) linking the two ferrocenyl units with the cobalt bis(dicarbollide) anion was synthesized by the reaction of a zinc derivative of ethynylferrocene with the diiodocobalt bis(dicarbollide) anion using Pd0 catalyst in 75 % yield. Complex 3 was unambiguously characterized by NMR and IR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. The X‐ray structure of 3 reveals that the two ferrocenyl units are perpendicular to each other with a total distance of 1.86 nm between the two Fe metal centers. The cyclic voltammogram of 3 shows a single oxidation potential corresponding to the two ferrocenyl units. Time‐dependent density functional theory (TD‐DFT) studies on complex 3 in tandem with UV/Vis spectroscopic analysis indicate the dominance of the dicarbollide moiety in the LUMOs, and HOMO→LUMO transitions at 435 nm illustrate the charge transfer from the two ferrocenyl units to the cobalt bis(dicarbollide) linker.

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Section: Resultssupporting

confidence: 64%

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

et al. 2018

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“…The determined in-plane hexagonal lattice parameter of 0.5 nm fits reasonably well with the 0.6 nm semiaxis length of the cobaltabisdicarbollide groups in a 2D close-packed structure]. 21 Interestingly, in addition to the central hexagon in Figure 16e ascribed to the 2D hexagonal lattice observed in Figure 16d, some extra points are distributed along the FFT diagonal. Far from being an artifact, these points arise from the structural asymmetry of the 7-compound due to the lateral bipyridine unit, which breaks the symmetry plane of the supramolecular packing and appears as the brighter edge of each molecular feature in Figure 16d…”

Section: Self-assembly Propertysupporting

confidence: 71%

Electron Accumulative Molecules

et al. 2018

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With the goal to produce molecules with high electron accepting capacity and low reorganization energy upon gaining one or more electrons, a synthesis procedure leading to the formation of a B-N(aromatic) bond in a cluster has been developed. The research was focused on the development of a molecular structure able to accept and release a specific number of electrons without decomposing or change in its structural arrangement. The synthetic procedure consists of a parallel decomposition reaction to generate a reactive electrophile and a synthesis reaction to generate the B-N(aromatic) bond. This procedure has paved the way to produce the metallacarboranylviologen [M(CBH)(CBH)-NCH-CHN-M'(CBH)(CBH)] (M = M' = Co, Fe and M = Co and M' = Fe) and semi(metallacarboranyl)viologen [3,3'-M(8-(NCH-CHN-1,2-CBH)(1',2'-CBH)] (M = Co, Fe) electron cumulative molecules. These molecules are able to accept up to five electrons and to donate one in single electron steps at accessible potentials and in a reversible way. By targeted synthesis and corresponding electrochemical tests each electron transfer (ET) step has been assigned to specific fragments of the molecules. The molecules have been carefully characterized, and the electronic communication between both metal centers (when this situation applies) has been definitely observed through the coplanarity of both pyridine fragments. The structural characteristics of these molecules imply a low reorganization energy that is a necessary requirement for low energy ET processes. This makes them electronically comparable to fullerenes, but on their side, they have a wide range of possible solvents. The ET from one molecule to another has been clearly demonstrated as well as their self-organizing capacity. We consider that these molecules, thanks to their easy synthesis, ET, self-organizing capacity, wide range of solubility, and easy processability, can find important application in any area where ET is paramount.

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“…[1][2][3][4][5] Among the various derivatives of carboranes, special attention is paid to p-complexes of transition metals with carborane ligands, called metallacarboranes. The most known of them, cobalt bis(dicarbollide) [3,3 0 -Co(1,2-C 2 B 9 H 11 ) 2 ] À attracts increasing interest from researchers working in various elds from medical chemistry to [6][7][8][9][10][11] materials science [12][13][14][15][16][17][18] to due to its extraordinary high stability, low toxicity 19 and almost unlimited possibilities for chemical modication. 20,21 Recently, we suggested that cobalt bis(dicarbollide) can be used as a structural element in the design of molecular switches.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and study ofC-substituted methylthio derivatives of cobalt bis(dicarbollide)

et al. 2020

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How to get the desired reduction voltage in a single framework! Metallacarborane as an optimal probe for sequential voltage tuning

Cited by 27 publications

References 28 publications

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

Electron Accumulative Molecules

Synthesis and study ofC-substituted methylthio derivatives of cobalt bis(dicarbollide)

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