US20080311401A1 - Nanoparticle of a Spin Transition Compound - Google Patents

Nanoparticle of a Spin Transition Compound Download PDF

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US20080311401A1
US20080311401A1 US12/096,746 US9674606A US2008311401A1 US 20080311401 A1 US20080311401 A1 US 20080311401A1 US 9674606 A US9674606 A US 9674606A US 2008311401 A1 US2008311401 A1 US 2008311401A1
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nanoparticles
oil
solution
preparation
surfactant
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Jean-Francois Letard
Olivier Nguyen
Nathalie Daro
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Centre National de la Recherche Scientifique CNRS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the present invention relates to a material composed of particles having nanometric dimensions essentially comprising a spin transition compound, to a process for the preparation of said material and to various applications of the material.
  • Such compounds can in particular be coordination complexes comprising one or more metal centers having a 3d 4 , 3d 6 or 3d 7 configuration, one or more nitrogenous ligands and one or more anions, such as described, for example, in EP-0 543 465, EP-0 666 561, EP-0 745 986 and EP-0 842 988.
  • EP-0 543 465 describes a process for the preparation of spin transition compounds and the use for information storage.
  • the process consists in bringing together, on the one hand, the ligand and, on the other hand, an iron salt in an acid solution, in allowing to react, in order to obtain a precipitate, and in recovering the precipitate in the powder form.
  • the complex obtained is reduced beforehand to a powder in order to be deposited on a support by various methods.
  • the compounds mentioned correspond to one of the following formulae:
  • EP-0 666 561 describes spin transition compounds which correspond to the formula Fe(II)(H-Trz) 3 (X) 2 in which Trz is 1,2,4-triazole and (X) 2 represents the anion (BF 4 ⁇ ) 2 , (ClO 4 ⁇ ) 2 , (Br ⁇ ) 2 , (Cl ⁇ ) 2 or (CO 3 2 ⁇ ). These compounds exhibit two crystalline phases, each having spin transitions associated with a change in color (white/pink) and for which the temperatures T 1/2 ⁇ and T 1/2 ⁇ are respectively less than and greater than ambient temperature.
  • the preparation process is analogous to that described in EP-0 543 465 above.
  • EP-0 745 986 describes compounds corresponding to a formula analogous to that of the compounds of EP-0 543 465, in which M is a metal ion of d 5 , d 6 or d 7 configuration, the ligand is a dialkylaminotriazole and the anion comprises a sulfitoaryl, sulfitoalkyl, sulfitoaryl halide or sulfitoalkyl halide group.
  • These specific compounds have a hysteresis amplitude of greater than 70° C. and a region of bistability centered exactly around ambient temperature. Said compounds are pink in the LS state and white in the HS state.
  • the process for the preparation of the compounds, described very briefly, is analogous to that described in EP-0 543 465 above.
  • EP-0 842 988 describes spin transition chemical compounds and their use in display devices where a temperature threshold is exceeded.
  • the compounds are formed by a network composed of molecules each formed by a metal-ligand complex and by an anion, and they comprise at least one water molecule bonded to the ligand via a hydrogen bond.
  • the metal is chosen from those which have a d 4 , d 5 , d 6 or d 7 configuration.
  • the ligand is 1,2,4-triazole carrying an R substituent comprising an OH group.
  • the anions are nitrate and tosylate derivatives.
  • the compounds corresponding to this definition have a temperature T 1/2 ⁇ of between 80 and 95° C. and a T 1/2 ⁇ of ⁇ 170° C.
  • the compounds can be used in particular in devices intended to detect an accidentally high (of the order of 80° C.) storage temperature in storage buildings or transportation vehicles.
  • the compounds are prepared by mixing a precursor of the metal center and a precursor of the ligand, at ambient temperature, and by removing the solvent by filtration after a precipitate has been obtained.
  • the compound is obtained in the pulverulent form.
  • thermochromic pigments in polymer films having a micrometric thickness or as data carrier in Microsystems, the carriers having to remain transparent.
  • the aim of the present invention is to provide a process for the direct production of nanoparticles formed of complexes of iron, of a triazole ligand and of at least one anion.
  • the subject matter of the present invention is consequently a material in the form of nanoparticles formed of complexes, a process for the production of said material and applications of said material.
  • the material according to the present invention is composed of nanometric particles essentially comprising a compound corresponding to the formula:
  • nanometric particles is understood to mean particles which have a mean diameter between 1 nm and 500 nm, more particularly between 1 and 100 nm. When w is respectively 3, 300 or 1500, the mean size of the particles is respectively approximately 1 nm, 100 nm or 500 nm.
  • a compound which corresponds to the above definition is capable of reversibly changing spin state when heated or when cooled, with a changing color associated with each change in spin.
  • R substituent is an alkyl group
  • it is preferably chosen from alkyl groups having from 1 to 8 carbon atoms, more particularly from 1 to 4 carbon atoms.
  • R 1 and R 2 represent, independently of one another, preferably H or an alkyl group having from 1 to 8 carbon atoms, more particularly from 1 to 4 carbon atoms.
  • Each of the anions X and Y can be a monovalent anion or a divalent anion.
  • the monovalent anion is chosen from BF 4 ⁇ , ClO 4 ⁇ , Br ⁇ , Cl ⁇ and NO 3 ⁇ .
  • the divalent anion is preferably chosen from SO 4 2 ⁇ and CO 3 2 ⁇ . The choice of the anions makes it possible to control the spin transition (in particular the abrupt nature, the presence of hysteresis and the position of the transition).
  • FIGS. 1 and 2 are TEM images of the [Fe(NH 2 Trz) 3 ](Br) 2 complex nanoparticles of Example 1 a very uniform structuring of the nanoparticles in the spherical form.
  • FIG. 3 is a TEM image of a polymer doped with nanometric particles of Example 1 demonstrating the transparency.
  • FIGS. 4 and 5 show that the spin transition particles synthesized by the process of the prior art do not have uniform structuring.
  • FIG. 6 shows the opaqueness generated by the introduction of micrometric particles of the prior art (even in small proportions) into a structuring polymer (of PVA type) which is originally transparent.
  • FIG. 7 shows the change in the signal for reflectivity R as a function of the temperature T for the complex of Example 5 (curve b) and for the material with the same formula obtained by conventional synthesis (curve a).
  • FIG. 8 shows the change in the reflectivity R as a function of the temperature T for the derivative Fe(NH 2 Trz) 3 (NO 3 ) 2 synthesized by the conventional route (a), by the reverse micelle route (b) (test No. 2 in table 1) and by the reverse micelle route with silica coating (c).
  • FIG. 9 is a TEM image of a silica coating around a spin transition nanoparticle.
  • FIGS. 10 a , 10 b , and 10 c show the change in the magnetic signal, expressed as product ⁇ M T, respectively for samples 7(1), 7(2) and 7(3) of Example 7.
  • the molar magnetic susceptibility ⁇ M , in cm 3 mol ⁇ 1 , multiplied by the temperature T in degrees K, is given on the ordinate and the temperature T in degrees K is given on the abscissa, for the materials for which w 3, 5 and 7.
  • FIGS. 11 a , 11 b , and 11 c illustrates the expanded formula of each of the materials constituting the samples 7(1), 7(2) and 7(3) of Example 7.
  • This silica shell with a size of a few nanometers, is reflected by a diffuse coating around the particle.
  • M acts as doping agent for the spin transition phenomenon of the compound [(Fe 1-y M y L 3 ) w L 3 ][X 2/x ] w .
  • An increase in y reduces the abrupt nature of the transition and the intensity of the pink color corresponding to the low spin state.
  • Mention may be made, as an example of metal M, of the zinc(II), manganese(II) nickel(II), and cobalt(II) ions.
  • z 0.
  • the choice of the anions X and Y makes it possible to adjust the spin transition temperature and to vary the abrupt nature of the spin transition. Mention may be made, as an example of mixture of anions, of the BF 4 and NO 3 pair, the Br and NO 3 pair, or the Cl and NO 3 pair.
  • the complex nanoparticles are coated with a silica film.
  • the material proposed is obtained from a solution of Fe(II) salt and optionally of a precursor of the metal M in a solvent or a mixture of solvents and from a solution of ligand R-Trz in a solvent or a mixture of solvents.
  • the preparation is carried out by a reverse micelle synthesis.
  • the process comprises the following stages:
  • composition of the oil possessing surfactant properties type can be either a composition obtained by addition of a surfactant to an oil or a single product having both surfactant properties and oil properties (such as the products sold under the names Lauropal®, Tergitol® or Ifralan®).
  • the size of the particles formed can be controlled in particular by the choice of the reaction temperature and/or of the duration of contacting of the two microemulsions prepared respectively during stages a) and b). All things otherwise being equal, an increase in the duration and/or in the temperature promotes an increase in the size of the final particles.
  • the preparation is carried out by a microemulsion synthesis.
  • the process comprises the following stages:
  • the proportions of solvent, of surfactant and of oil which are required in order to obtain a microemulsion are determined from the phase diagram of the ternary mixture.
  • the ternary phase diagram is available in the literature for numerous solvent/oil/surfactant combinations. The determination of a specific ternary diagram is within the scope of a person skilled in the art.
  • a silyl derivative is added to the reaction medium, before denaturation of the micelle or of the microemulsion (that is to say, before stage d) in the two embodiments described above).
  • silyl derivative of tetraethoxysilane, (n-octadecyl)triethoxysilane and (n-octyl)triethoxysilane.
  • the material in the form of nanoparticles of the present invention is of particular use as thermochromic pigment.
  • thermochromic pigment By way of example, in the field of plastics technology, the application of a varnish is often carried out in the form of a layer with a thickness of a few microns.
  • the nanoparticles proposed can be incorporated directly into a polymer matrix which will be applied to a substrate in the form of a layer with a thickness of the order of a micrometer, whereas, in the prior art, a preliminary stage in which microparticles of spin transition material are ground is necessary.
  • the material in the form of nanoparticles according to the invention is in addition of use for data storage.
  • the nanoparticles constitute a true “molecular memory” using the phenomenon of spin transition. A bit of information can thus be stored in each nanoparticle.
  • the perfect transparency of a disk composed of a polymer matrix built with these bistable nanoparticles makes it possible to envisage applications in the field of bulk data storage (holography).
  • the significant modification in color (that is to say of the absorption spectrum) associated with the phenomenon of spin transition is reflected by a change in the refractive index of the material between the low spin state and the high spin state.
  • the respective refractive indices of the two states can be adjusted in order to render the medium transparent when the molecules are in the HS state.
  • the photo-induced effects can bring about switching from the HS state to the LS state and can thus bring about a variation in the refractive index.
  • the initially transparent medium then becomes opaque. This phenomenon makes possible the use of the nanoparticles in the field of optical limiters and also as optical gate for data storage.
  • Nanoparticles of a material having a magnetic response which changes with temperature from a diamagnetic form (LS state) to a paramagnetic form (HS state) can be used for the preparation of heat-sensitive contrast agents for thermotherapy methods.
  • the nanoparticles, positioned in situ, would make it possible to monitor the crossing of a temperature threshold, such as that which distinguishes healthy cells from cancer cells. This is because the magnetic resonance image (MRI) of a medium comprising the nanoparticles is normal in the case of the nanoparticles in the diamagnetic low spin state and highly distorted in the case of a paramagnetic high spin state.
  • MRI magnetic resonance image
  • a material was prepared by an inverse emulsion synthesis according to the following procedure.
  • the compounds are dissolved in the two round-bottomed flasks by mechanical stirring in a water bath at 50° C. Subsequently, m 5 g of surfactant (Lauropal 205 or Ifralan D205 or Tergitol, which act both as surfactant and as oily phase) are added.
  • surfactant Liscosorbal 205 or Ifralan D205 or Tergitol, which act both as surfactant and as oily phase
  • the round-bottomed flasks A and B are subsequently subjected to mixing using a vortex mixer, which generates vigorous mechanical stirring favorable for the formation of micelles.
  • the two reverse micelles thus obtained are thermodynamically stable for several minutes.
  • the contents of the round-bottomed flask B are rapidly added to the contents of the round-bottomed flask A and then the combined mixture is subjected to mixing using a vortex mixer for several minutes in order to promote micelle exchange.
  • the particles are finally obtained by addition of diethyl ether, which has the effect of denaturing the reverse micelle.
  • the diethyl ether dissolves the surfactant and not the complex formed. After centrifuging and removing the liquid phase, the washing operation is repeated an additional 3 to 4 times until the supernatant liquid is perfectly clear.
  • FIGS. 1 , 2 and 3 TEM images of the [Fe(NH 2 Trz) 3 ](Br) 2 complex nanoparticles obtained in tests No. 1 are represented in FIGS. 1 , 2 and 3 .
  • the images of FIGS. 1 and 2 show a very uniform structuring of the nanoparticles in the spherical form. This structure results from the fact that the synthetic reaction is confined to nanodroplets.
  • the size of the particles is of the order of 100 nm, which typically corresponds to a value of 300 for w in the formula (I).
  • the transparency of a polymer doped with nanometric particles is demonstrated in FIG. 3 .
  • FIGS. 4 , 5 and 6 show that the spin transition particles synthesized by the process of the prior art do not have uniform structuring.
  • the grains are nonuniform and have a size of the order of 60 ⁇ m.
  • the opaqueness generated by the introduction of micrometric particles (even in small proportions) into a structuring polymer (of PVA type) which is originally transparent is shown in FIG. 6 .
  • a material was prepared by a microemulsion synthesis under the following conditions.
  • the two clear solutions were subsequently mixed and this new mixture was subjected to ultrasound until a clear final solution was obtained.
  • Analyses by light scattering showed particles of the order of 3 nm, which typically corresponds to a value of 9 for w in the formula (I).
  • the clear solution is pink in the low spin state and white in the high spin state. This reversible modification in the color from pink to white by a change in the temperature demonstrates that the spin transition phenomenon occurs on the scale of the nanomaterial in situ.
  • the particles are finally obtained by addition of ethanol, the effect of which is to denature the inverse microemulsion.
  • the ethanol dissolves the surfactant and not the complex formed. After centrifuging and removing the liquid phase, the washing operation is repeated 3 to 4 times until the supernatant liquid is perfectly clear.
  • Nanoparticles were prepared starting from an Fe precursor and an M precursor by an inverse emulsion synthesis under the conditions of test No. 3 given in table 1, 0.116 g of FeCl 2 and 0.124 g of ZnCl 2 , in place of 0.21 g of FeCl 2 , being introduced into the round-bottomed flask A. Nanoparticles formed by the Fe 0.5 Zn 0.5 Cl 2 complex were obtained. The size of the particles is of the order of 100 nm, i.e. typically a w of 300.
  • Example 2 The procedure of example 2 was repeated, the FeBr 2 solution being replaced with an FeCl 2 and ZnCl 2 solution. Nanoparticles formed by the Fe 0.5 Zn 0.5 Cl 2 complex were obtained. The size of the particles is of the order of 100 nm, i.e. typically a w of 300.
  • example 1 The procedure of example 1 was repeated under the following conditions, Fe(BF 4 ) 2 being dissolved in the Fe(NO 3 ) 2 solution.
  • Nanoparticles of an [Fe(NH 2 TrZ) 3 (NO 3 ) 1.7 (BF 4 ) 0.3 ] complex were obtained.
  • the size of the particles is of the order of 100 nm, i.e. typically a w of 300.
  • a material was prepared with a silica coating by a reverse micelle synthesis according to the procedure of example 1 carried out with the precursor FeBr 2 .
  • the difference from example 1 lies in the fact that, after having mixed the two micelle solutions and stirred using a vortex mixer for a few minutes, 2 ml of tetraethoxysilane (TEOS) were added.
  • TEOS tetraethoxysilane
  • the change in the reflectivity R as a function of the temperature T for the derivative Fe(NH 2 Trz) 3 (NO 3 ) 2 synthesized by the conventional route (a), by the reverse micelle route (b) (test No. 2 in table 1) and by the reverse micelle route with silica coating (c) is shown in FIG. 8 .
  • the TEM image of a silica coating around a spin transition nanoparticle is represented in FIG. 9 . This silica shell, with a size of a few nanometers, is reflected by a diffuse coating around the particle.
  • solution A A solution of m 1 g of FeBr 2 in 0.342 g of water and a solution of 0.8 g of AOT in 23 ml of n-heptane were prepared, then the two solutions were mixed and the mixture thus obtained was subjected to ultrasound until a clear solution was obtained, this solution being referred to as solution A.
  • solution B A solution of m 2 g of NH 2 Trz in 0.342 g of water and a solution of 0.8 g of AOT in 23 ml of n-heptane were prepared, then the two solutions were mixed and the mixture thus obtained was subjected to ultrasound until a clear solution was obtained, this solution being referred to as solution B.
  • Solutions A and B were subsequently mixed and this new mixture was subjected to ultrasound until a clear final solution was obtained.
  • the particles were obtained according to the procedure of example 2, by addition of and washing with ethanol.
  • the change in the magnetic signal, expressed as product ⁇ M T, respectively for samples 7(1), 7(2) and 7(3) is shown in FIGS. 10 a, b and c .
  • the curves confirm the presence of a gradual spin transition for the three nanomaterials about 300 K.
  • the expanded formulae for the samples 7(1), 7(2) and 7(3) respectively are represented in FIGS. 11 a, b and c.
  • the size of the particles ⁇ (in nm), the corresponding value of w and the theoretical magnetic value at 350 K ⁇ M T (in cm 3 mol ⁇ 1 K) are given in the following table.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compounds Of Iron (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Luminescent Compositions (AREA)
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FR0512476A FR2894581B1 (fr) 2005-12-08 2005-12-08 Nanoparticules d'un compose a transition de spin
PCT/FR2006/002651 WO2007065996A1 (fr) 2005-12-08 2006-12-05 Nanoparticules d'un compose a transition de spin

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US20100178511A1 (en) * 2007-06-12 2010-07-15 Centre National De La Recherche Scientifique Spin transition material
US20130214179A1 (en) * 2010-07-22 2013-08-22 Centre National De La Recherche Scientifique Method for the thermal photoswitching of spin-transition materials, and uses thereof
JP2013538884A (ja) * 2010-07-22 2013-10-17 サントゥル ナシオナル ドゥ ラ ルシェルシュ シアンティフィック − セーエヌエールエス 可逆性インクを用いて表面を印刷する方法
US20130306936A1 (en) * 2011-02-07 2013-11-21 Centre National De La Recherche Scientifique - Cnrs - Optimized arrangement of triazole particles
EP3173455A1 (fr) 2015-11-30 2017-05-31 The Swatch Group Research and Development Ltd. Élément d'habillage avec capteur de température
CN111479483A (zh) * 2017-12-21 2020-07-31 斯沃奇集团研究和开发有限公司 用于钟表或珠宝的外部部件
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FR2941458B1 (fr) 2009-01-28 2011-02-25 Centre Nat Rech Scient Nouveau materiau a transition de spin, son procede de preparation
WO2011125837A1 (ja) * 2010-03-31 2011-10-13 日油技研工業株式会社 温度管理インジケータ及びそれが付された構造物
FR2993888B1 (fr) * 2012-07-30 2015-11-27 Inst Polytechnique Bordeaux Materiau composite thermochrome et procede de fabrication d'un tel article
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US8753743B2 (en) 2014-06-17
FR2894581A1 (fr) 2007-06-15
JP5340740B2 (ja) 2013-11-13
EP1960410B1 (fr) 2010-03-03
US20130011680A1 (en) 2013-01-10
DE602006012730D1 (de) 2010-04-15
FR2894581B1 (fr) 2008-02-22
EP1960410A1 (fr) 2008-08-27
JP2009519879A (ja) 2009-05-21

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