0000000001311138
AUTHOR
Rosario Núñez
showing 31 related works from this author
Synthesis of small carboranylsilane dendrons as scaffolds for multiple functionalizations.
2006
Small carbosilane dendrons in which a closo-carborane is located at the focal point have been prepared by a sequence of steps involving hydrosilylation and reduction reactions. These compounds are used as scaffolds for peripheral functionalization with styrene, chlorovinylstyrene, or suitable carboranes, while keeping the C(cluster)-Si (C(c)-Si) bond. Modification of the core by reduction of the carborane with Mg/BrCH2CH2Br was also achieved.
Carborane-stilbene dyads: influence of substituents and cluster isomers on the photoluminescence properties
2017
Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (Cc) with either a methyl (Me), or a phenyl (Ph) group, are introduced herein alongside with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds has been prepared from styrenecontaining carborane derivatives via Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd2(dba)3]/[Pd(t-Bu3P)2] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterized and the crystal structures of seven of them analyzed by X-ray diffraction. Th…
Controlled Direct Synthesis of C-Mono- and C-Disubstituted Derivatives of [3,3′-Co(1,2-C2B9H11)2]− with Organosilane Groups: Theoretical Calculations…
2008
Mono- and dilithium salts of [3,3'-Co(1,2-C(2)B(9)H(11))(2)](-), (1(-)), react with different chlorosilanes (Me(2)SiHCl, Me(2)SiCl(2), Me(3)SiCl and MeSiHCl(2)) with an accurate control of the temperature to give a set of novel C(c)-mono- (C(c) = C(cluster)) and C(c)-disubstituted cobaltabis(dicarbollide) derivatives with silyl functions: [1-SiMe(2)H-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (3(-)); [1,1'-mu-SiMe(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (4(-)); [1,1'-mu-SiMeH-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (5(-)); [1-SiMe(3)-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))](-) (6(-)) and [1,1'-(SiMe(3))(2)-3,3'-Co(1,2-C(2)B(9)H(10))(2)](-) (7(-)). In a similar way, the [8,8'-mu-(1''…
Modular Construction of Neutral and Anionic Carboranyl-Containing Carbosilane-Based Dendrimers
2007
A modular construction of new carbosilane dendrimers, which contain four and eight peripheral carborane derivatives and propyl linkages between the C cluster and the Si atoms, has been developed using different methodologies. Regiospecific hydrosilylation of 1-C 6 H 5 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (1) and 1-CH 3 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (2) offers an efficient route to molecular precursors and building blocks that can provide both divergent and convergent strategies for dendritic growth. First generations of neutral carboranyl-containing dendrimers were constructed by two approaches: (a) a divergent approach via hydrosilylation of 1 and 2 with the first genera…
Formation of New η5-Rhodium(III) Complexes from η5-Rh(I) Rhodacarborane-Containing Charge-Compensated Ligands
2004
A series of new Rh(I) half-sandwich complexes of formula [3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 1 0 )] (L = SMe 2 (2a), SEt 2 (2b), S(CH 2 ) 4 (2c), SEtPh (2d)) and [1-Me-3,3-(PPh 3 ) 2 -8-L-closo-3,1,2-RhC 2 B 9 H 9 )] (L = SMe 2 (2e), SEt 2 (2f)) have been prepared by reaction of the respective monoanionic charge-compensated ligands [10-L-nido-7,8-C 2 B 9 H 1 0 ] - and [7-Me-10-L-7,8-C 2 B 9 H 9 ] - with [RhCl(PPh 3 ) 3 ]. Complex [3,3-(cod)-8-SMe2-closo-3,1,2-RhC 2 B 9 H 1 0 ] (3) has also been prepared by reaction of K[10-SMe 2 -nido-7,8-C 2 B 9 H 1 0 ] with [RhCl(cod)] 2 . Rh(I) complexes 2a-d may be easily oxidized to the corresponding Rh(III) complexes 4a-d under N 2 atmosphere…
Synthesis and fluorescence emission of neutral and anionic di- and tetra-carboranyl compounds
2011
A new family of photoluminescent neutral and anionic di-carboranyl and tetra-carboranyl derivatives have been synthesized and characterized. The reaction of α,α'-bis(3,5-bis(bromomethyl)phenoxy-m-xylene with 4 equiv. of the monolithium salt of 1-Ph-1,2-C(2)B(10)H(11) or 1-Me-1,2-C(2)B(10)H(11) gives the neutral tetracarboranyl-functionalized aryl ether derivatives closo-1 and closo-2, respectively. The addition of the monolithium salt of 1-Ph-1,2-closo-C(2)B(10)H(11) to α,α,'-dibromo-m-xylene or 2,6-dibromomethyl-pyridine gives the corresponding di-carboranyl derivatives closo-3 and closo-4. These compounds, which contain four or two closo clusters, were degraded using the classical method,…
Carboranyl Substituted Siloxanes and Octasilsesquioxanes: Synthesis, Characterization, and Reactivity
2008
Carboranyl-containing disiloxane, cyclic-siloxane and cage-like silsesquioxane have been prepared in high yields. Two routes are compared for their preparation, a classical hydrolytic process based on hydrolysis and condensation of the freshly prepared carboranylalkylchlorosilane and ethoxysilane precursors and a nonhydrolytic route based on the specific reactivity of chorosilane toward DMSO. Based on the typical reactivity of the carboranyl group toward nucleophiles, dianionic disiloxanes and octaanionic silsesquioxanes were obtained without modification of the siloxane bond. Products are fully characterized by FTIR, NMR and MALDI-TOF methods.
Fluorescence of Newo-Carborane Compounds with Different Fluorophores: Can it be Tuned?
2014
Two sets of o-carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene-containing carboranes 6-9, was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1-[(9,9-dioctyl-fluorene-2-yl)ethynyl]carborane (11) was synthesized by the reaction of 9,9-dioctyl-2-ethynylfluorene and decaborane (B10H14). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4-(chloromethyl)styrene or 9-(chloromethyl)anthracene yielded compounds 12 and 13. Members of the se…
A versatile methodology for the controlled synthesis of photoluminescent high-boron-content dendrimers.
2013
Fluorescent star-shaped mol- ecules and dendrimers with a 1,3,5-tri- phenylbenzene moiety as the core and 3 or 9 carborane derivatives at the pe- riphery, have been prepared in very good yields by following different ap- proaches. One procedure relies on the nucleophilic substitution of Br groups in 1,3,5-tris(4-(3-bromopropoxy)phe- nyl)benzene with the monolithium salts of methyl and phenyl-o-carborane. The second method is the hydrosilylation reactions on the peripheral allyl ether functions of 1,3,5-tris(4-allyloxy-phe- nyl)benzene and 1,3,5-tris(4-(3,4,5-tris- AAA with suitable carboranyl-silanes to produce different generations of dendrimers decorated with carboranyl fragments. This ap…
Approaches to the preparation of carborane-containing carbosilane compounds.
2005
[Structure: see text] A novel type of carborane cluster assembly has been successfully prepared using carbosilane derivatives as a scaffold. Two synthetic routes have been used: One involves the reaction of a carbosilane containing terminal Si-Cl functions with the lithium salt of the phenyl-o-carborane, and the second one consists of a highly efficient hydrosilylation of tetravinylsilane with the corresponding carboranylsilane. The crystal structure of this carborane-containing carbosilane compound has been determined by X-ray diffraction.
Influence of the solvent and R groups on the structure of (carboranyl)R2PI2 compounds in solution. Crystal structure of the first iodophosphonium sal…
2008
The influence of the electron-donor or electron-acceptor capacity of the R groups (R = (i)Pr, Ph, Et) and the solvent on the molecular geometry in solution of adducts of carboranylphosphanes [(carboranyl)(i)Pr2P, (carboranyl)Ph2P and (carboranyl)Et2P] with I2 in 1 : 1 ratios, has been studied in detail by 31P{1H} and 11B{1H} NMR spectroscopies. The more electron-accepting Ph groups make the (carboranyl)Ph2P less nucleophilic, thus stabilizing the I2 encapsulated neutral biscarboranylphosphane-diiodine adducts in solution, such as (carboranyl)Ph2PI-IPPh2(carboranyl), generating P---I-I---P motifs. Even in a polar solvent, such as EtOH, the arrangement is preserved. The expected basicity of t…
Synthesis and Characterization of New Fluorescent Styrene-Containing Carborane Derivatives: The Singular Quenching Role of a Phenyl Substituent
2011
A set of neutral and anionic carborane derivatives in which the styrenyl fragment is introduced as a fluorophore group has been successfully synthesized and characterized. The reaction of the monolithium salts of 1-Ph-1,2-C(2)B(10)H(11), 1-Me-1,2-C(2)B(10)H(11) and 1,2-C(2)B(10)H(12) with one equivalent of 4-vinylbenzyl chloride leads to the formation of compounds 1-3, whereas the reaction of the dilithium salt of 1,2-C(2)B(10)H(12) with two equivalents of 4-vinylbenzyl chloride gives disubstituted compound 4. The closo clusters were degraded using the classical method, KOH in EtOH, to afford the corresponding nido species, which were isolated as tetramethylammonium salts. The crystal struc…
Highly Stable Neutral and Positively Charged Dicarbollide Sandwich Complexes
2005
Novel sandwich metallacarboranes commo-[3,3'-Ni(8-SMe2-1,2-C2B9H10)2] (1), commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2]+ (2+), commo-[3,3'-Ru(8-SMe2-1,2-C2B9H10)2] (4) and commo-[3,3'-Fe(8-SMe2-1,2-C2B9H10)2] (5) have been prepared by reaction of [10-SMe2-7,8-nido-C2B9H10]- with NiCl2 x 6 H2O, CoCl2, [RuCl2(dmso)4] and [FeCl2(dppe)], respectively. Reduction of 2+ with metallic Zn leads to the neutral and isolable complex commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2] (3). Theoretical calculations using the ZINDO/1 semiempirical method show three energy minima for complexes 1-3 and 5 that agree with the presence of three different rotamers in solution at low temperature, while four relative energy minima have…
Recent studies on RR′S·C2B9H11 charge-compensated ligands
2002
Abstract In this paper we report the synthesis of three new carborane derivatives of the series 7,8-R,R′-10-L-7,8-C2B9H9 (R=R′=H, L=SEtPh; R=CH3, R′=H, L=SMe2 and L=SEt2) along with the enhanced characterization of formerly described compounds 7,8-R,R′-10-L-7,8-C2B9H9 (R=R′=H, L=SMe2 (1), L=SEt2 (2) and L=S(CH2)4 (3)). They have been fully characterised using 1H-, 11B- and 13C-NMR spectroscopy. Their bridging proton resonances have been located for the first time. Individual sulfonium substituent contributions have been calculated that have permitted to establish a rule to predict its position in the 1H-NMR spectrum. The crystal structures of 1 and 3 have been resolved for the first time. T…
Tetrakis{[(p-dodecacarboranyl)methyl]stilbenyl}ethylene: A Luminescent Tetraphenylethylene (TPE) Core System
2017
The synthesis and spectroscopic characterization of the first set of tetra(p-dodecacarborane-stilbeno)ethylenes (TDSE), substituted either with a methyl or phenyl group in the 2-position (Ccluster) of the ortho-carborane, are described. The complex absorption properties are elucidated by TD-DFT calculations, stressing the importance of through bond conjugation. Enhanced conjugation and restriction of the conformational space are identified as the main factors for boosted luminescence properties in solution compared to tetraphenylethylene (TPE) core, effectively reducing internal conversion (IC). IC is further reduced when aggregate suspensions of our compounds in water are formed, providing…
Photoluminescence in Carborane–Stilbene Triads : A Structural, Spectroscopic, and Computational Study
2016
A set of triads in which o- and m-carborane clusters are bonded to two stilbene units through Ccluster -CH2 bonds was synthesized, and their structures were confirmed by X-ray diffraction. A study on the influence of the o- and m- isomers on the absorption and photoluminescence properties of the stilbene units in solution revealed no charge-transfer contributions in the lowest excited state, as confirmed by (TD)DFT calculations. The presence of one or two B-I groups in m-carborane derivatives does not affect the emission properties of the stilbenes in solution, probably due to the rather large distance between the iodo substituents and the fluorophore. Nevertheless, a significant redshift o…
The Role of C–H···H–B Interactions in Establishing Rotamer Configurations in Metallabis(dicarbollide) Systems
2010
The aim of this work is to explore the self-interaction capability of the anion [3,3′-Co(1,2-C2B9H11)2]– through Ccluster–H···H–B (Cc–H···H–B) dihydrogen bonds. A set of theoretical and empirical data aiming to establish the main rules that account for the binding mode between the negatively charged borane framework made by [3,3′-Co(1,2-C2B9H11)2]– and the [NMe4]+ ions have been compiled. The interaction between cation and anion is mainly electrostatic but the covalent contribution is also proven and quantified. The existing intermolecular H···H short contacts have been studied and are compared with available data from the Cambridge Structural Database. The results show that the electronic …
A Discrete P⋅⋅⋅II⋅⋅⋅P Assembly: The Large Influence of Weak Interactions on the31P NMR Spectra of Phosphane–Diiodine Complexes
2006
Thioethers, except derivatives of [7-R-7,8-C2B9H11] , are more weakly coordinating ligands than phosphanes. This difference is evidenced by the I I distances in the spokeshaped charge-transfer (CT) complexes R2S·I2 and R3P·I2 (Figure 1). The I I distance is sensitive to the strength of the interaction between the s* LUMO orbital on I2 and the HOMO orbital of the donor atom: the stronger the donor, the longer the I I distance. In these spoke CT complexes, the I I distance varies from 3.2 0.2 7 in R3P·I2 adducts [5] to 2.80 0.05 7 in R2S·I2 adducts, [6] indicating the weaker donor character of the thioether group. Whereas extended I2 arrays, spoke adducts of I2, polyiodides, and other structu…
CCDC 1425778: Experimental Crystal Structure Determination
2015
Related Article: Arántzazu González-Campo, Emilio José Juárez-Pérez, Clara Viñas, Bruno Boury, Reijo Sillanpää, Raikko Kivekäs and Rosario Núñez|2008|Macromolecules|41|8458|doi:10.1021/ma801483c
CCDC 1569221: Experimental Crystal Structure Determination
2017
Related Article: Justo Cabrera-González, Clara Viñas, Matti Haukka, Santanu Bhattacharyya, Johannes Gierschner, Rosario Núñez|2016|Chem.-Eur.J.|22|13588|doi:10.1002/chem.201601177
CCDC 986488: Experimental Crystal Structure Determination
2014
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CCDC 986493: Experimental Crystal Structure Determination
2014
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CCDC 1569224: Experimental Crystal Structure Determination
2017
Related Article: Justo Cabrera-González, Clara Viñas, Matti Haukka, Santanu Bhattacharyya, Johannes Gierschner, Rosario Núñez|2016|Chem.-Eur.J.|22|13588|doi:10.1002/chem.201601177
CCDC 986492: Experimental Crystal Structure Determination
2014
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CCDC 1569223: Experimental Crystal Structure Determination
2017
Related Article: Justo Cabrera-González, Clara Viñas, Matti Haukka, Santanu Bhattacharyya, Johannes Gierschner, Rosario Núñez|2016|Chem.-Eur.J.|22|13588|doi:10.1002/chem.201601177
CCDC 1569222: Experimental Crystal Structure Determination
2017
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CCDC 986490: Experimental Crystal Structure Determination
2014
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CCDC 986489: Experimental Crystal Structure Determination
2014
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CCDC 986491: Experimental Crystal Structure Determination
2014
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CCDC 906346: Experimental Crystal Structure Determination
2013
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CCDC 713126: Experimental Crystal Structure Determination
2011
Related Article: Emilio José Juárez-Pérez, Rosario Núñez, Clara Viñas, Reijo Sillanpää, Francesc Teixidor|2010|Eur.J.Inorg.Chem.|2010|2385|doi:10.1002/ejic.201000157