WO2005092906A1 - Metalodendrites - Google Patents
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- WO2005092906A1 WO2005092906A1 PCT/ES2005/000150 ES2005000150W WO2005092906A1 WO 2005092906 A1 WO2005092906 A1 WO 2005092906A1 ES 2005000150 W ES2005000150 W ES 2005000150W WO 2005092906 A1 WO2005092906 A1 WO 2005092906A1
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- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
Definitions
- the invention relates in general to new hyperbranched molecules that incorporate metals in their structure, called metallodendrites, whose conformation changes reversibly against a red-ox stimulus. Also, the invention relates to its use as molecular switches.
- Hyperbranched macromolecules called dendrimers, that incorporate one or more metals in their structure have specific physicochemical characteristics that allow them to be easily used as molecular switches.
- the interest in their development is based on the ability to obtain highly ordered materials with magnetic, electronic and optical properties of technological interest, and in this sense, in their use as molecular switches.
- the term molecular switch is defined as a set of discrete molecular systems that allow mechanical movements (output) when subjected to an external stimulus (input).
- This metallodendrite has a number of drawbacks, such as its very limited solubility to certain solvents or reaction media. Therefore it cannot be used in solution in any reaction medium in which it is not soluble. Likewise, this metallodendrite is not stable in all the reaction media in which it could be used, and the variation it suffers from its molecular dimensions in response to a red-ox stimulus is not sufficiently marked.
- the present invention faces the problem of providing an alternative metallodendrite that overcomes part or all of the disadvantages of the prior art metallodendrite, mentioned above.
- the solution provided by the present invention is based on the fact that the inventors have observed that, on the one hand it is possible to modulate the solubility in the different solvents of the metallodendrites by introducing groups or substituents, which do not produce a steric impediment that prevents their change conformational Likewise, the inventors have surprisingly observed that when the ferrocene elements are placed, in addition to the periphery, a much more drastic, unidirectional conformational change occurs in the center of the structure.
- the invention provides a new metallodendrite selected from the group of metallodendrites A) with a two-dimensional, symmetrical structure (Formula 1) and the group of metallodendrites B) that in addition to the ferrocenes in said hyper-branching comprise a ferrocene central (Formula 2).
- a new metallodendrite selected from the group of metallodendrites A) with a two-dimensional, symmetrical structure (Formula 1) and the group of metallodendrites B) that in addition to the ferrocenes in said hyper-branching comprise a ferrocene central (Formula 2).
- SUBSTITUTE SHEET (RULE 26) group A) because they have a larger central core, such as those of group B) due to the presence of a central ferrocene, have a larger molecular size and a response in the most drastic conformational change. Additionally, metallodendrites with a central ferrocene of group B) undergo a 100% unidirectional conformational change, which greatly increases their possibility of response.
- Figure 1 Represents the synthesis scheme of a metallodendrite of group B) and the reversible conformational change that it undergoes against a red-ox stimulus.
- the present invention provides a metallodendrite selected from group A) or B) where: the metallodendrites of group A) have the formula 1:
- SUBSTITUTE SHEET (RULE 26) where, one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group consisting of halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR, - CHO, -S0 3 H, -CN, -COR, -CH 2 NR ⁇ R 2 where R is selected from the group consisting of linear, branched and cyclic C ⁇ -C 6 alkyl groups, and where Rl and R2 can be independently the same or different with each other, hydrogen or an R group;
- Fe is the structure ( ⁇ 5 -C 5 H 5 ) -M- ( ⁇ 5 -C 5 H) -, where M is a metal coordinated to the two cyclopentadienyl rings ( ⁇ 5 -C 5 H 5 ) and ( ⁇ 5- C 5 H), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr,
- one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group consisting of halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR, -CHO , -SO 3 H, -CN, -COR, -CE2NR 1 R 2 where R is selected from the group consisting of linear, branched and cyclic Ci-C ⁇ alkyl groups, and where Rl and R2 can be independently the same or different from each other , hydrogen or an R group;
- Fe is the structure ( ⁇ 5 -C 5 H 5 ) -M- ( ⁇ 5 -C5H 4 ) - 5 where M is a metal coordinated to the two cyclopentadienyl rings ( ⁇ 5 -C 5 H 5 ) and ( ⁇ 5 -C 5 H 4 ), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; and the central iron atom may be a metal other than Fe selected from Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V.
- the substituents on the metallodendrite of group A) or on the metallodendrite of group B) are preferably substituents that do not imply steric impediments in their conformational change, and that may impair their ability to undergo a maximum conformational change.
- Fe represents ferrocene-ferrocinium.
- the metallodendrite of group B) has a Fe atom in the center of it.
- the red-ox stimulus is any combination of an oxidizing agent and a reducing agent, so that the oxidizing agent is capable of oxidizing the metallodendrite, in particular, the metal atoms from an initial oxidation state to a higher oxidation state and Then, the reducing agent is able to reduce the metal atoms to the starting oxidation state.
- SUBSTITUTE SHEET (RULE 26)
- the type of conformational change undergone by a metallodendrite of group A) is two-dimensional resulting in an elongation of the ramifications.
- group B metallodendrites see Figure 1
- this change is much more drastic, since the central ferrocene structural element - ( ⁇ 5 -C 5 H 4 ) -M- ( ⁇ 5 -C 5 H 4 ) -, rotates on itself, as a hinge, causing an anti conformation, fully expanded in only one direction.
- the conformational changes have been verified by spectroscopic characterization techniques, in particular nuclear magnetic resonance imaging (NMR) and X-ray diffraction.
- NMR nuclear magnetic resonance imaging
- the metallodendrites of group B) have two identical branches, which overlap so that the benzenes also overlap contributing to their great stability in their folded conformation. Said overlapping of the benzene rings stabilize the structure by means of pi-pi interactions. The greater the number of benzene rings in each branch, the greater the stability of the metallodendrite.
- the metallodendrites are obtained by the general procedure described in the aforementioned reference characterized by the use of the catalyst sin-di (m-chloro) -bis [o- (benzylphenylphosphine) benzyl] dipaladium (II). Two particular embodiments of the method of obtaining are described below (see Examples 1 and 2). Any variant for another particular embodiment is evident to a person skilled in the art in view of the aforementioned document and common general knowledge.
- the metallodendrites of the invention have application as molecular switches.
- the applications of these new metallodendrites derive from their particular properties, since they offer the possibility of preparing conjugated systems that offer the possibility of electronic communication between the terminal subunits, this being of particular interest in terms of modulating electronic properties of the materials.
- its use stands out as a sensor of red-ox processes, for example, as a sensor of the presence of carbon monoxide.
- its use can also be mentioned in the design of machines on a molecular scale, in molecular detection systems, design of chemically controlled switches, storage of information, among others.
- the reaction crude was taken to dryness under reduced pressure (13 mm Hg) and an extraction was carried out with H 2 O / NaHCO 3 and CH C1.
- the organic phase was dried over MgSO 4 and purified by column chromatography with silica gel, using as eluent a mixture of hexane and CH C1 2 in a 1: 1 ratio. The yield was 80%.
Abstract
The invention relates to novel hyperbranched molecules, the structure of which incorporates metals known as metalodendrites, having a conformation which changes in a reversible manner in response to a redox stimulus, and to the use of same as molecular switches. Said metalodendrites preferably contain structural ferrocene/ferrocenium units.
Description
METALODENDRITAS METALODENDRITAS
CAMPO DE LA INVENCIÓN La invención se relaciona en general con nuevas moléculas hiperramificadas que incorporan metales en su estructura, denominadas metalodendritas, cuya conformación cambia de forma reversible frente a un estímulo red-ox. Asimismo, la invención se relaciona con su empleo como interruptores moleculares.FIELD OF THE INVENTION The invention relates in general to new hyperbranched molecules that incorporate metals in their structure, called metallodendrites, whose conformation changes reversibly against a red-ox stimulus. Also, the invention relates to its use as molecular switches.
ANTECEDENTES DE LA INVENCIÓNBACKGROUND OF THE INVENTION
Las macromoléculas hiperramificadas, denominadas dendrímeros, que incorporan uno o más metales en su estructura presentan características físico- químicas específicas que permiten que sean fácilmente empleadas como interruptores moleculares. El interés en el desarrollo de las mismas se basa en la capacidad de obtener materiales altamente ordenados con propiedades magnéticas, electrónicas y ópticas de interés tecnológico, y en este sentido, en su empleo como interruptores moleculares. El término interruptor molecular se define como un conjunto de sistemas moleculares discretos que permite realizar movimientos mecánicos (output) cuando son sometidos a un estímulo externo (input).Hyperbranched macromolecules, called dendrimers, that incorporate one or more metals in their structure have specific physicochemical characteristics that allow them to be easily used as molecular switches. The interest in their development is based on the ability to obtain highly ordered materials with magnetic, electronic and optical properties of technological interest, and in this sense, in their use as molecular switches. The term molecular switch is defined as a set of discrete molecular systems that allow mechanical movements (output) when subjected to an external stimulus (input).
El documento Peruga, A., et al., J. Organometallic Chem., 637-639 (2001) 191-197, "Facile synthesis of bidimensional ferrocenyl-based branched oligomers by palladium-catalyzed coupling reactions", describe un procedimiento para la síntesis de una metalodendrita. Dicha metalodendrita es un complejo metálico bidimensional en forma de estrella, que frente a un estímulo red-ox aumenta sus dimensiones moleculares estirándose por la repulsión que se produce entre los ferrocenos que contienen átomos de Fe2+ y que son oxidados a Fe3+. Esta metalodendrita presenta una serie de inconvenientes, tales como su solubilidad muy limitada a determinados disolventes o medios de reacción. Por tanto no puede ser utilizada en disolución en cualquier de medio de reacción en la que ésta no sea soluble. Asimismo, esta metalodendrita no es estable en todos los medios de reacción en los que podría utilizarse, y la variación que sufre de sus dimensiones moleculares en respuesta a un estímulo red-ox no es suficientemente marcada.Peruga, A., et al., J. Organometallic Chem., 637-639 (2001) 191-197, "Facile synthesis of two-dimensional ferrocenyl-based branched oligomers by palladium-catalyzed coupling reactions", describes a procedure for the synthesis of a metallodendrite. Said metallodendrite is a two-dimensional metal complex in the form of a star, which in the face of a red-ox stimulus increases its molecular dimensions by stretching out the repulsion that occurs between ferrocenes that contain Fe 2+ atoms and that are oxidized to Fe 3+ . This metallodendrite has a number of drawbacks, such as its very limited solubility to certain solvents or reaction media. Therefore it cannot be used in solution in any reaction medium in which it is not soluble. Likewise, this metallodendrite is not stable in all the reaction media in which it could be used, and the variation it suffers from its molecular dimensions in response to a red-ox stimulus is not sufficiently marked.
HOJA DE SUSTITUCIÓN (REGLA 26)
Sería importante conseguir interruptores moleculares fáciles de síntesis, solubles en diferentes medios y que presenten una significativa variación, por ejemplo en sus dimensiones, frente variaciones redox. Existe por lo tanto la necesidad de proporcionar, metalodendritas alternativas que superen parte o la totalidad de los inconvenientes del estado de la técnica y que por lo tanto puedan tener una aplicación industrial.SUBSTITUTE SHEET (RULE 26) It would be important to achieve molecular switches that are easy to synthesize, soluble in different media and that have a significant variation, for example in their dimensions, against redox variations. There is therefore a need to provide alternative metallodendrites that overcome part or all of the drawbacks of the prior art and therefore may have an industrial application.
COMPENDIO DE LA INVENCIÓNSUMMARY OF THE INVENTION
La presente invención se enfrenta al problema de proporcionar una metalodendrita alternativa que supere parte o la totalidad de los inconvenientes de la metalodendrita del estado de la técnica, mencionados anteriormente. La solución aportada por la presente invención se basa en que los inventores han observado que, por una parte es posible modular la solubilidad en los distintos disolventes de las metalodendritas mediante la introducción de grupos o sustituyentes, que no producen un impedimento estérico que impida su cambio conformacional. Asimismo, los inventores han observado sorprendentemente que cuando los elementos ferroceno se colocan, además de en la periferia, en el centro de la estructura se produce un cambio conformacional mucho más drástico, unidireccional.The present invention faces the problem of providing an alternative metallodendrite that overcomes part or all of the disadvantages of the prior art metallodendrite, mentioned above. The solution provided by the present invention is based on the fact that the inventors have observed that, on the one hand it is possible to modulate the solubility in the different solvents of the metallodendrites by introducing groups or substituents, which do not produce a steric impediment that prevents their change conformational Likewise, the inventors have surprisingly observed that when the ferrocene elements are placed, in addition to the periphery, a much more drastic, unidirectional conformational change occurs in the center of the structure.
Por lo tanto en un aspecto la invención proporciona una nueva metalodendrita seleccionada entre el grupo de las metalodendritas A) con una estructura bidimensional, simétrica (Fórmula 1) y el grupo de las metalodendritas B) que adicionalmente a las ferrocenos en dichas hiperrramificaciones comprenden un ferroceno central (Fórmula 2). Entre las ventajas de las nuevas metalodendritas puede mencionarse la posibilidad de seleccionar una determinada metalodendrita con unas características de solubilidad determinadas dependiendo del medio de reacción en el que se desee aplicar. Otra ventaja adicional de estas metalodendritas consiste en que tanto las deTherefore, in one aspect the invention provides a new metallodendrite selected from the group of metallodendrites A) with a two-dimensional, symmetrical structure (Formula 1) and the group of metallodendrites B) that in addition to the ferrocenes in said hyper-branching comprise a ferrocene central (Formula 2). Among the advantages of the new metallodendrites can be mentioned the possibility of selecting a certain metallodendrite with certain solubility characteristics depending on the reaction medium in which it is desired to apply. Another additional advantage of these metallodendrites is that both those of
HOJA DE SUSTITUCIÓN (REGLA 26)
grupo A), por tener un mayor "core" central, como las del grupo B) por la presencia de un ferroceno central, presentan un mayor tamaño molecular y una respuesta en el cambio conformacional más drástico. Adicionalmente, las metalodendritas con un ferroceno central del grupo B) sufren un cambio conformacional unidireccional del 100%, lo que aumenta su posibilidad de respuesta enormemente.SUBSTITUTE SHEET (RULE 26) group A), because they have a larger central core, such as those of group B) due to the presence of a central ferrocene, have a larger molecular size and a response in the most drastic conformational change. Additionally, metallodendrites with a central ferrocene of group B) undergo a 100% unidirectional conformational change, which greatly increases their possibility of response.
BREVE DESCRIPCIÓN DE LAS FIGURASBRIEF DESCRIPTION OF THE FIGURES
Figura 1. Representa el esquema de síntesis de una metalodendrita del grupo B) y el cambio conformacional reversible que sufre frente a un estímulo red-ox.Figure 1. Represents the synthesis scheme of a metallodendrite of group B) and the reversible conformational change that it undergoes against a red-ox stimulus.
DESCRIPCIÓN DE LA INVENCIÓN La presente invención proporciona una metalodendrita seleccionada del grupo A) ó B) donde: las metalodendritas del grupo A) presentan la fórmula 1 :DESCRIPTION OF THE INVENTION The present invention provides a metallodendrite selected from group A) or B) where: the metallodendrites of group A) have the formula 1:
Fórmula 1Formula 1
HOJA DE SUSTITUCIÓN (REGLA 26)
donde, uno o más de los sustituyentes hidrógenos presentes en la misma pueden ser independientemente sustituidos por uno o más sustituyentes seleccionados del grupo formado por halógenos, grupos R, arilo, -OH, -OR, -COOH, -COOR, -OCOR, -CHO, -S03H, -CN, -COR, -CH2NRιR2 donde R se selecciona del grupo formado por los grupos alquilo Cι-C6 lineal, ramificado y cíclico, y donde Rl y R2 pueden ser independientemente iguales o diferentes entre sí, hidrógeno o un grupo R; Fe es la estructura (η5-C5H5)-M-(η5-C5H )-, donde M es un metal coordinado a los dos anillos de ciclopentadienilo (η5-C5H5) y (η5-C5H ), seleccionado entre Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V; y las metalodendritas del grupo B) presentan la fórmula estructural siguiente:SUBSTITUTE SHEET (RULE 26) where, one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group consisting of halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR, - CHO, -S0 3 H, -CN, -COR, -CH 2 NRιR 2 where R is selected from the group consisting of linear, branched and cyclic Cι-C 6 alkyl groups, and where Rl and R2 can be independently the same or different with each other, hydrogen or an R group; Fe is the structure (η 5 -C 5 H 5 ) -M- (η 5 -C 5 H) -, where M is a metal coordinated to the two cyclopentadienyl rings (η 5 -C 5 H 5 ) and (η 5- C 5 H), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; and the metallodendrites of group B) have the following structural formula:
Formula 2Formula 2
donde uno o más de los sustituyentes hidrógenos presentes en la misma pueden ser independientemente sustituidos por uno o más sustituyentes seleccionados del grupo formado por halógenos, grupos R, arilo, -OH, -OR, -COOH, -COOR, -OCOR, -CHO,-SO3H, -CN, -COR, -CE2NR1R2 donde R se selecciona del grupo formado por los grupos alquilo Ci-Cβ lineal, ramificado y cíclico, y donde Rl y R2 pueden ser independientemente iguales o diferentes entre sí, hidrógeno o un grupo R;where one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group consisting of halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR, -CHO , -SO 3 H, -CN, -COR, -CE2NR 1 R 2 where R is selected from the group consisting of linear, branched and cyclic Ci-Cβ alkyl groups, and where Rl and R2 can be independently the same or different from each other , hydrogen or an R group;
HOJA DE SUSTITUCIÓN (REGLA 26)
Fe es la estructura (η5-C5H5)-M-(η5-C5H4)-5 donde M es un metal coordinado a los dos anillos de ciclopentadienilo (η5-C5H5) y (η5-C5H4), seleccionado entre Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V; y el átomo de hierro central puede ser un metal distinto del Fe seleccionado entre Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V. Asimismo, el número de unidades estructurales [-CH=CH-C6C4-], es decir de anillos benceno separados por dobles enlaces C=C, en dichas ramificaciones puede estar comprendido entre 1 y 5.SUBSTITUTE SHEET (RULE 26) Fe is the structure (η 5 -C 5 H 5 ) -M- (η 5 -C5H 4 ) - 5 where M is a metal coordinated to the two cyclopentadienyl rings (η 5 -C 5 H 5 ) and (η 5 -C 5 H 4 ), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; and the central iron atom may be a metal other than Fe selected from Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V. Also, the number of structural units [-CH = CH-C 6 C 4 -], that is of benzene rings separated by double bonds C = C, in said branches it can be comprised between 1 and 5.
Los sustituyentes sobre la metalodendrita del grupo A) o sobre la metalodendrita del grupo B) son preferentemente sustituyentes que no impliquen impedimentos estéricos en el cambio conformacional de las mismas, y que puedan mermar su capacidad de sufrir un cambio conformacional máximo.The substituents on the metallodendrite of group A) or on the metallodendrite of group B) are preferably substituents that do not imply steric impediments in their conformational change, and that may impair their ability to undergo a maximum conformational change.
En una realización particular Fe representa ferroceno-ferrocinio. En otra realización particular, la metalodendrita del grupo B) presenta un átomo de Fe en el centro de la misma.In a particular embodiment, Fe represents ferrocene-ferrocinium. In another particular embodiment, the metallodendrite of group B) has a Fe atom in the center of it.
Estas nuevas metalodendritas proporcionadas por la presente invención, en adelante metalodendritas de la invención, reaccionan de forma reversible frente a un estímulo red-ox. El estímulo red-ox es cualquier combinación de un agente oxidante y un agente reductor, de modo que el agente oxidante sea capaz de oxidar la metalodendrita, en particular, los átomos de metal desde un estado de oxidación inicial a un estado de oxidación superior y, a continuación, el agente reductor sea capaz de reducir los átomos de metal al estado de oxidación de partida. La oxidación de dichos átomos de metal provoca un aumento de la carga positiva en la metalodendrita y esto conduce a una fuerte repulsión electrostática entre ellas, que conduce a un significativo aumento del tamaño de la misma y al cambio conformacional para minimizar dichas repulsiones. Este tipo de metalodendritas que reaccionan de forma reversible se utilizan como interruptores moleculares. Dicha reversibilidad ha sido comprobada mediante estudios de voltametría cíclica.These new metallodendrites provided by the present invention, hereinafter metallodendrites of the invention, react reversibly against a red-ox stimulus. The red-ox stimulus is any combination of an oxidizing agent and a reducing agent, so that the oxidizing agent is capable of oxidizing the metallodendrite, in particular, the metal atoms from an initial oxidation state to a higher oxidation state and Then, the reducing agent is able to reduce the metal atoms to the starting oxidation state. The oxidation of said metal atoms causes an increase in the positive charge on the metallodendrite and this leads to a strong electrostatic repulsion between them, which leads to a significant increase in the size of the metal and conformational change to minimize such repulsions. These types of metallodendrites that react reversibly are used as molecular switches. This reversibility has been verified by cyclic voltammetry studies.
HOJA DE SUSTITUCIÓN (REGLA 26)
El tipo de cambio conformacional que sufre una metalodendrita del grupo A) es bidimensional dando lugar a una elongación de las ramificaciones. En las metalodendritas del grupo B) (ver Figura 1) dicho cambio es mucho más drástico, puesto que el elemento estructural central ferroceno -(η5-C5H4)-M-(η5-C5H4)-, gira sobre sí mismo, a modo de una bisagra, originando una conformación anti, totalmente expandida en una sola dirección. Los cambios conformacionales han sido comprobados mediante técnicas de caracterización espectroscópica, en particular, resonancia magnética nuclear (RMN) y difracción de rayos-X. Las metalodendritas del grupo B) presentan dos ramificaciones idénticas, que se solapan de modo que los bencenos se solapan igualmente contribuyendo a una gran estabilidad de las mismas en su conformación plegada. Dicho solapamiento de los anillos bencénicos estabilizan la estructura mediante interacciones de tipo pi-pi. A mayor número de anillos benceno en cada ramificación mayor es la estabilidad de la metalodendrita. Las metalodendritas se obtienen mediante el procedimiento general descrito en la referencia mencionada caracterizado por el empleo del catalizador sin-di(m- cloro)-bis[o-(bencilfenilfosfina)bencil]dipaladio (II). Dos realizaciones particulares del procedimiento de obtención se describen posteriormente (ver Ejemplos 1 y 2). Cualquier variante para otra realización particular resulta evidente para un experto en la materia a la vista del documento mencionado y el conocimiento general común.SUBSTITUTE SHEET (RULE 26) The type of conformational change undergone by a metallodendrite of group A) is two-dimensional resulting in an elongation of the ramifications. In group B metallodendrites (see Figure 1) this change is much more drastic, since the central ferrocene structural element - (η 5 -C 5 H 4 ) -M- (η 5 -C 5 H 4 ) -, rotates on itself, as a hinge, causing an anti conformation, fully expanded in only one direction. The conformational changes have been verified by spectroscopic characterization techniques, in particular nuclear magnetic resonance imaging (NMR) and X-ray diffraction. The metallodendrites of group B) have two identical branches, which overlap so that the benzenes also overlap contributing to their great stability in their folded conformation. Said overlapping of the benzene rings stabilize the structure by means of pi-pi interactions. The greater the number of benzene rings in each branch, the greater the stability of the metallodendrite. The metallodendrites are obtained by the general procedure described in the aforementioned reference characterized by the use of the catalyst sin-di (m-chloro) -bis [o- (benzylphenylphosphine) benzyl] dipaladium (II). Two particular embodiments of the method of obtaining are described below (see Examples 1 and 2). Any variant for another particular embodiment is evident to a person skilled in the art in view of the aforementioned document and common general knowledge.
Las metalodendritas de la invención tienen aplicación como interruptores moleculares. Las aplicaciones de estas nuevas metalodendritas derivan de las propiedades particulares de las mismas, ya que ofrecen la posibilidad de preparar sistemas conjugados que ofrezcan la posibilidad de la comunicación electrónica entre las subunidades terminales, siendo esto de interés particular en términos de modular propiedades electrónicas de los materiales. Entre las aplicaciones de las metalodendritas de la invención destaca su utilización como sensor de procesos red- ox, por ejemplo, como sensor de la presencia de monóxido de carbono. Entre otras aplicaciones puede citarse asimismo su utilización en el diseño de máquinas a escala molecular, en sistemas de detección molecular, diseño de interruptores químicamente controlados, almacenamiento de información, entre otros.The metallodendrites of the invention have application as molecular switches. The applications of these new metallodendrites derive from their particular properties, since they offer the possibility of preparing conjugated systems that offer the possibility of electronic communication between the terminal subunits, this being of particular interest in terms of modulating electronic properties of the materials. Among the applications of the metallodendrites of the invention, its use stands out as a sensor of red-ox processes, for example, as a sensor of the presence of carbon monoxide. Among other applications, its use can also be mentioned in the design of machines on a molecular scale, in molecular detection systems, design of chemically controlled switches, storage of information, among others.
HOJA DE SUSTITUCIÓN (REGLA 26)
Los siguientes Ejemplos ilustrativos de la invención no deben ser interpretados como limitativos del ámbito de protección de la misma.SUBSTITUTE SHEET (RULE 26) The following illustrative Examples of the invention should not be construed as limiting the scope of protection thereof.
EJEMPLOS Ejemplo 1 Síntesis de Fe"! (η5-C5H4)-CH=CH-C6H4-CH=CH-C6H3[-CH=CH-(η5-C5H4)2]2f-2EXAMPLES Example 1 Synthesis of Faith "! (Η 5 -C 5 H 4 ) -CH = CH-C 6 H4-CH = CH-C6H 3 [-CH = CH- (η 5 -C5H 4 ) 2] 2 f- two
Una suspensión de la olefina l,3-bis-<i -CH=CH-(η5-C5H4)-Fe -(η5-C5H5) }'-5- CH2=CH-C6H3 (200 mg, 0,4 mmol), Fe"!
(105 mg, 0,2 m ol), acetato sódico anhidro (40 mg, 0,6 mmol), bromuro de tetrabutilamonio (40 mg, 0,2 mmol) y 20 mg de sin-di(m-cloro)-bis[o-(bencilfenilfosfina)bencil]dipaladio (II) en DMA (N,N-dimetilcetamida) (12 mi) se calentó a 130°C durante 5 h. El crudo de la reacción se llevó a sequedad bajo presión reducida (13 mm Hg) y se realizó una extracción con agua/diclorometano. La fase orgánica se secó sobre sulfato magnésico y se purificó mediante cromatografía de columna con gel de sílice utilizando como eluyente una mezcla de hexano/diclorometano en relación 2:1. El producto fue recristalizado utilizando una mezcla de diclorometano/hexano. El rendimiento fue del 62%. En la Figura 1 se representa esquematizada la síntesis de dicho compuesto del grupo de metalodendritas B), junto con el cambio conformacional que sufre dicha metalodendrita en presencia de un estímulo red-ox.A suspension of olefin l, 3-bis- < i -CH = CH- (η 5 -C 5 H 4 ) -Fe - (η 5 -C 5 H 5 )} '- 5- CH 2 = CH-C 6 H 3 (200 mg, 0.4 mmol), Fe "! (105 mg, 0.2 m ol), anhydrous sodium acetate (40 mg, 0.6 mmol), tetrabutylammonium bromide (40 mg, 0.2 mmol) and 20 mg of sin-di (m-chloro) -bis [o- (benzylphenylphosphine) benzyl] dipaladium (II) in DMA (N, N-dimethylcetamide) (12 ml) was heated at 130 ° C for 5 h. The reaction crude was brought to dryness under reduced pressure (13 mm Hg) and an extraction with water / dichloromethane was performed. The organic phase was dried over magnesium sulfate and purified by silica gel column chromatography using as eluent a mixture of hexane / dichloromethane in a 2: 1 ratio. The product was recrystallized using a dichloromethane / hexane mixture. The yield was 62%. The synthesis of said compound of the group of metallodendrites B) is shown schematically in Figure 1, together with the conformational change that said metallodendrite undergoes in the presence of a red-ox stimulus.
HOJA DE SUSTITUCIÓN (REGLA 26)
SUBSTITUTE SHEET (RULE 26)
HOJA DE SUSTITUCIÓN (REGLA 26)
Ejemplo 2SUBSTITUTE SHEET (RULE 26) Example 2
Síntesis de (E,E EM)-{((ηηss--CC55HH5)Fe(ηs-C5H4)-CH=CH-(ηS-C5H4)Fe(η5-CsH4)-
Synthesis of (E, E MS) - {((ηη ss --CC 5 5HH 5 ) Fe (η s -C 5 H 4 ) -CH = CH- (η S -C 5 H 4 ) Fe (η 5 - CsH 4 ) -
Una suspensión de 0,5 mmol de (E)-(η5-C5H5)Fe(η5-C5H4)-CH=CH-(η5-C5H4)Fe(η5- C5H4)-CH=CH2, 0,6 mmol de l,3,5-(4-bromofenil)benceno, 2,6 mmol de acetato sódico anhidro, 0,2 mmol de bromuro de tetrabutilamonio y 0,02 mmol de sin-di(m- cloro)-bis[o-(bencilfenilfosfina)bencil]dipaladio (II) en DMF (N,N- dimetilformamida) se calentó a 130 °C durante 20 horas. El crudo de la reacción se llevó a sequedad bajo presión reducida (13 mm Hg) y se realizó una extracción con H2O/NaHCO3 y CH C1 . La fase orgánica se secó sobre MgSO4 y se purificó mediante cromatografía de columna con gel de sílice, usando como eluyente una mezcla de hexano y CH C12 en relación 1:1. El rendimiento fue del 80%.A suspension of 0.5 mmol of (E) - (η 5 -C 5 H 5 ) Fe (η 5 -C 5 H 4 ) -CH = CH- (η 5 -C 5 H 4 ) Fe (η 5 - C 5 H 4 ) -CH = CH 2 , 0.6 mmol of l, 3.5- (4-bromophenyl) benzene, 2.6 mmol of anhydrous sodium acetate, 0.2 mmol of tetrabutylammonium bromide and 0.02 mmol of sin-di (m-chloro) -bis [o- (benzylphenylphosphine) benzyl] dipaladium (II) in DMF (N, N-dimethylformamide) was heated at 130 ° C for 20 hours. The reaction crude was taken to dryness under reduced pressure (13 mm Hg) and an extraction was carried out with H 2 O / NaHCO 3 and CH C1. The organic phase was dried over MgSO 4 and purified by column chromatography with silica gel, using as eluent a mixture of hexane and CH C1 2 in a 1: 1 ratio. The yield was 80%.
HOJA DE SUSTITUCIÓN (REGLA 26)
SUBSTITUTE SHEET (RULE 26)
Claims
1. Una metalodendrita seleccionada entre el grupo de metalodendritas A) de fórmula estructural:1. A metallodendrite selected from the group of metallodendrites A) of structural formula:
Fórmula 1 donde, uno o más de los sustituyentes hidrógenos presentes en la misma pueden ser independientemente sustituidos por uno o más sustituyentes seleccionados del grupo fomiado por halógenos, grupos R, arilo, -OH, -OR, -COOH, -COOR, -OCOR, -CHO,-SO3H, -CN, -COR, -CH2NR1R2 donde R se selecciona del grupo formado por los grupos alquilo Cι-C6 lineal, ramificado y cíclico, y donde Rl y R2 pueden ser independientemente iguales o diferentes entre sí, hidrógeno o un grupo R; yFormula 1 where, one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group fused by halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR , -CHO, -SO 3 H, -CN, -COR, -CH 2 NR 1 R 2 where R is selected from the group consisting of linear, branched and cyclic Cι-C 6 alkyl groups, and where Rl and R2 can be independently equal or different from each other, hydrogen or an R group; Y
Fe es la estructura (η5-C5H5)-M-(η5-CsH4)-, donde M es un metal coordinado a los dos anillos de ciclopentadienilo (η5-C5H5) y (η5-C5H4), seleccionado entre Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V; yFe is the structure (η 5 -C 5 H 5 ) -M- (η 5 -CsH 4 ) -, where M is a metal coordinated to the two cyclopentadienyl rings (η 5 -C 5 H 5 ) and (η 5 -C 5 H 4 ), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; Y
HOJA DE SUSTITUCIÓN (REGLA 26) una metalodendrita del grupo B) de fórmula estructural:SUBSTITUTE SHEET (RULE 26) a metallodendrite of group B) of structural formula:
Formula 2Formula 2
donde uno o más de los sustituyentes hidrógenos presentes en la misma pueden ser independientemente sustituidos por uno o más sustituyentes seleccionados del grupo formado por halógenos, grupos R, arilo, -OH, -OR, -COOH, -COOR, -OCOR, -CHO. -SO3H, -CN, -COR, -CH2N _ 2 donde R se selecciona del grupo formado por los grupos alquilo Cι-C6 lineal, ramificado y cíclico, y dónele Rl y R2 pueden ser independientemente iguales o diferentes entre sí, hidrógeno o un grupo R; Fe es la estructura (η5-C5H5)-M-(η5-C5H4)-, donde M es un metal coordinado a los dos anillos de ciclopentadienilo (r^-CsHs) y (η5-C5H4), seleccionado entre Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V; el átomo de hierro central puede ser un metal distinto del Fe seleccionado entre Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W y V; y el número de unidades estructurales [-CH=CH-C6C -j, está comprendido entre 1 y 5.where one or more of the hydrogenic substituents present therein can be independently substituted by one or more substituents selected from the group consisting of halogens, R groups, aryl, -OH, -OR, -COOH, -COOR, -OCOR, -CHO . -SO 3 H, -CN, -COR, -CH 2 N _ 2 where R is selected from the group consisting of linear, branched and cyclic Cι-C 6 alkyl groups, and where Rl and R2 can be independently the same or different between yes, hydrogen or an R group; Fe is the structure (η 5 -C 5 H 5 ) -M- (η 5 -C 5 H 4 ) -, where M is a metal coordinated to the two cyclopentadienyl rings (r ^ -CsHs) and (η 5 - C 5 H 4 ), selected from Fe, Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; the central iron atom may be a metal other than Fe selected from Ni, Co, Zr, Ru, Cr, Zr, Hf, Ti, Mo, Nb, W and V; and the number of structural units [-CH = CH-C 6 C -j, is between 1 and 5.
2. Una metalodendrita según la reivindicación 1, donde Fe representa ferroceno-ferricinio.2. A metallodendrite according to claim 1, wherein Fe represents ferrocene-ferricinium.
HOJA DE SUSTITUCIÓN (REGLA 26) SUBSTITUTE SHEET (RULE 26)
3. Una metalodendrita según la reivindicación 1, donde en la estructura la metalodendrita del grupo B) presenta un átomo de Fe en el centro de la misma.3. A metallodendrite according to claim 1, wherein in the structure the metallodendrite of group B) has a Fe atom in the center thereof.
4. Empleo de una metalodendrita según la reivindicación 1, como interruptor molecular.4. Use of a metallodendrite according to claim 1, as a molecular switch.
5. Empleo de una metalodendrita según la reivindicación 1, como sensor para la detección de monóxido de carbono.5. Use of a metallodendrite according to claim 1, as a sensor for the detection of carbon monoxide.
6. Empleo de una metalodendrita según la reivindicación 1, en el diseño de máquinas a escala molecular, en sistemas de detección molecular, diseño de interruptores químicamente controlados, y/o almacenamiento de información.6. Use of a metallodendrite according to claim 1, in the design of machines on a molecular scale, in molecular detection systems, design of chemically controlled switches, and / or information storage.
HOJA DE SUSTITUCIÓN (REGLA 26) SUBSTITUTE SHEET (RULE 26)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ESP200400714 | 2004-03-23 | ||
| ES200400714A ES2239901B1 (en) | 2004-03-23 | 2004-03-23 | METALODENDRITAS. |
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|---|---|---|---|
| PCT/ES2005/000150 WO2005092906A1 (en) | 2004-03-23 | 2005-03-22 | Metalodendrites |
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| WO (1) | WO2005092906A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2454366A (en) * | 2007-11-01 | 2009-05-06 | Univ Cranfield | Electrochemical mediators |
| US8003221B2 (en) * | 2006-11-13 | 2011-08-23 | Samsung Electronics Co., Ltd. | Metallocenyl dendrimer, organic memory device using the same and fabrication method of the organic memory device |
| US8124238B2 (en) * | 2007-04-02 | 2012-02-28 | Samsung Electronics Co., Ltd. | Dendrimer having metallocene core, organic memory device using the same and manufacturing method thereof |
-
2004
- 2004-03-23 ES ES200400714A patent/ES2239901B1/en not_active Withdrawn - After Issue
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2005
- 2005-03-22 WO PCT/ES2005/000150 patent/WO2005092906A1/en active Application Filing
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8003221B2 (en) * | 2006-11-13 | 2011-08-23 | Samsung Electronics Co., Ltd. | Metallocenyl dendrimer, organic memory device using the same and fabrication method of the organic memory device |
| US8124238B2 (en) * | 2007-04-02 | 2012-02-28 | Samsung Electronics Co., Ltd. | Dendrimer having metallocene core, organic memory device using the same and manufacturing method thereof |
| KR101458204B1 (en) * | 2007-04-02 | 2014-11-04 | 삼성전자주식회사 | Dendrimer having metallocene core, organic memory device using the same and preparation method thereof |
| GB2454366A (en) * | 2007-11-01 | 2009-05-06 | Univ Cranfield | Electrochemical mediators |
| GB2454366B (en) * | 2007-11-01 | 2012-01-04 | Univ Cranfield | Polydisperse hyperbranched polymers with redox mediator moieties and their uses |
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| Publication number | Publication date |
|---|---|
| ES2239901B1 (en) | 2006-12-01 |
| ES2239901A1 (en) | 2005-10-01 |
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