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    • 专利摘要:
    Molecular nanocapsules for the selective separation of fullerenes. Molecular nanocapsules formed by self-assembly and based on tetracarboxylated (metallo) porphyrins and metal macrocyclic compounds, linked through m-carboxylate bond, and counterions, in addition to their use for the purification and/or selective separation of fullerenes. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2547720A1
    申请号:ES201430315
    申请日:2014-03-07
    公开日:2015-10-08
    发明作者:Xavi RIBAS SALAMAÑA；Miquel Costas Salgueiro；Cristina GARCÍA SIMÓN；Anna Company Casadevall；Laura GÓMEZ MARTÍN
    申请人:Universitat de Girona；
    IPC主号:
    专利说明:

    The present invention relates to molecular nanocapsules formed byself-assembly and based on complexes and metalloporphyrins and their use forpurification and / or selective separation of fulerenes.
    STATE OF THE TECHNIQUE
    The fulerenes are nanometric molecules (-1 nm in diameter) with applications in a wide range of fields from the science of materials to their use in drugs. Today, the derivatives of fulerene are the reference type n materials for the construction of organic photovoltaic devices. The search for molecular receptors 15 for fulerenes, essentially for C60, began in the 1990s to be able to have minimum quantities that allowed characterizing the properties of the material. From the point of view of molecular recognition, fulerenes are very peculiar host molecules. Its unusual shape (approximately spherical, maximizing the surface / volume ratio) and its chemical nature 20 (non-polarized polyenes) restrict the types of non-covalent forces that can be
    used for their association with dispersion forces (Tt-n and van der Waals).
    The separation and purification of fulerenes from mixtures with other allotropic forms of carbon is an unsolved problem. There is great interest in overcoming the tedious and difficult chromatographic extractions that are currently used to separate the most common fulerenes purely. Among them, C60 and C70 are the best known and studied precisely because of their greater availability, although their cost continues to be high or very high due to the need for large amounts of solvents used in chromatographic purification processes. In addition, the separation and purification of larger fulerenes, larger than C70 (known as "fullerenes") is today the biggest problem for the study of their properties. For the separation and purification of "higher fullerenes" the classical chromatographic methods are unacceptable due to their low solubility and the many necessary chromatographic cycles, reasons for the
    35 which study of these compounds is clearly underdeveloped.
    As an alternative to chromatographic extractions in recent years, two types of strategies have been used for encapsulation of fulerenes: a) the use of host molecules of a completely organic nature and with apolar groups (aromatic rings) of suitable dimensions for encapsulation of fulerenes , Y
    5 b) the use of hosts containing transition metals.
    In both approaches, the subsequent release of the host is achieved by
    various forms: a) acid-base treatment to achieve the opening of the capsule and
    precipitation of the fulerene, b) the use of external physical stimuli (irradiation with
    10 light) non-invasive at room temperature and c) moving the fulerene with a substrate with greater affinity towards the host.
    There are selective host-host systems for C60, such as cyclodextrins or calix [8] arenes. In these systems the release of the fulerene is difficult because of its high stability (Atwood, J.L .; Koutsantonis, G.A. and Raston, C.IL Nature, 368, 229 (1994)).
    There are some exceptions, such as the calix [5] double sands developed byFukazawa et al., Capable of extracting C94 and C96 from mixtures of fulerenes. These
    20 host-host systems treated at temperatures above 100 ° C allow the release of the aforementioned fulerenes due to a conformational change of the host. However, these hosts cannot be reused for the same application (Haino, T.; Fukunaga, C .; Fukazawa, Y. Org. Lett., 8, 3545-3548 (2006)).
    On the other hand, the dimeric cyclic systems of Aida et al., Which contain two porphyrinic units, are capable of extracting fulerenes greater than C76 from mixtures of fulerenes. Through the use of more selective hosts for these systems, such as 4,4'-bipyridine, the authors demonstrate the obtaining of mixtures enriched with "higher fullerens" (for example of mixtures C1 02-C11 O) and without a trace of the majority
    30 C60 and C70. (Shoji, Y .; Tashiro, K .; Aida, T. J. Am. Chem. Soc., 126, 6570-6571 (2004)).
    In addition, Mendoza et al. Has developed a supramolecular system based on cyclotriveratrylene receptors containing three 4-ureidopyrimidinone (UPy) and 35 units that self-assemble using hydrogen bridge bonds. The authors have shown that this system is capable of encapsulating preferably C84 by
    in front of C70 and far ahead of C60 due to the different association constants. The release of the fulerenes is carried out by treatment with trifluoroacetic acid of solutions of the host-host system in THF (tetrahydrofuran), causing precipitation of the fulerenes in question. (Huerta, E .;
    5 Metselaar, G.A .; Fragoso, A; Santos, E .; Bo, C. and de Mendoza, J. Angew. ChemInt. Ed., 46, 202-205 (2007); Huerta, E .; eequier, E. and de Mendoza, J. ehem.Commun., 5017-5018 (2007 ». A similar strategy has been developed by Zhanget al. (Zhang, e.; Wang, Q .; Long, H. and Zhang, W. J. Am. Ehem. Soc., 133, 51(2011)).
    10 Therefore, there is great interest in developing hosts capable of encapsulating and releasing selectively and differently controlled fulerenes of different sizes.
    15 DESCRIPTION OF THE INVENTION
    The present invention relates to the synthesis of molecular nanocapsules based on self-assembly by means of coordination chemistry of metal macrocyclic compounds with tetracarboxylated (metallo) porphyrins, and their use as sponges of 20 fulerenes of different dimensions. The nanocapsules obtained are tetragonal prismatic in nature with a large interior space capable of encapsulating a molecule of fulerene of different dimensions. The possibility of varying the design within the same family of nanocapsules allows to have a technology to encapsulate and release selectively and at will
    25 fulerenos of a certain size.
    The nanocapsules of the present invention have advantages in different aspects of the separation and purification of fulerenes. The use of a ligand with n = 2 provides the ability to absorb inside it from C60 to C84. The use of a ligand
    30 with n = 1 it is expected to be effective for the absorption of small size “C60), while ligands with n = 3 would be effective for the absorption of larger size (> C84).
    The nature of these nanocapsules is highly modular and simply, the use of different metals in porphyrin is understood as an element that will allow and modify the affinity of the fulerenes for the capsules. Finally the
    octacathonic nature of nanocapsules and the use of different counterions
    they constitute elements of system versatility that must allow the use of capsules in different solvents.
    5 Therefore, a first aspect of the present invention relates to a nanocapsuleformed by two parallel (metal) tetracarboxylated porphyrins of general formula (1)joined by four metal macrocyclic compounds of general formula (11) throughof an M-carboxylate bond, and counterions (X) in a number suitable for
    compensate for the octacathic charge of the nanocapsule.
    10 or
    or
    ~"" "~
    d
    ~
    ~
    R,
    ~ ~
    "" "
    or R, ~ 01 / '¡, A
    N "N
    M --- ~ ~ R)
    , 7 CI R) (:, I # 'R,,
    / R'n
    M ~ "- / T" N
    o ~ R! l /! J "R,
    or
    (1) (11)
    where: M 'is selected from the list comprising 2H, Zn, Cu, FeCI, Ir, Pd, Pt, Ag,
    15 AuCI, Ni, Ru, Al, Pb, SnCI "InCI, SbCI, TiO, lrCI" CrCI and va; preferably M 'is 2H, ln, Cu, FeCI, Ir, Pt, Ag, AuCl, Ni, Ru, Al, Pb, SnCI "InCI, SbCI, TiO, l rCI" CrCI and va;
    M is a metal that is selected from the list comprising Pd, Cu, Pt, Ni and Zn; each R1 and each ~ independently represent a hydrogen or a
    20 halogen;
    each R2 and each R3 independently represent a hydrogen or a group
    alkyl (C, -C,);n has a value of 1, 2 or 3.
    By "compliment us" in the present invention is meant a bromine, chlorine, iodine or fluorine atom. Preferably it is fluorine.
    The term "alkyl" refers in the present invention to aliphatic, linear or branched chains, having 1 to 7 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, s-butyl, n-pentyl, etc. Preferably it has 1 to 4 carbon atoms, more preferably methyl, ethyl, n-propyl, i-propyl or t-butyl and even more preferably it is methyl.
    By "fulerene" is meant in the present invention a molecular form of carbon, with a carbon number equal to greater than 20 and which can be classified by the number of carbons in: small fulerenes, below C60; standard bellows, which would be C60 and C70; and big fulerenos, older than C70. As fulerenos we also refer to endofulerenes and functionalized fulerenes. Endofulerenes are fulerenes that contain encapsulated metal particles or other molecules, can have the following formula: M "m @ Cn; where M" is a particle, preferably La, Sc, Ce, N, SC3N, LU3N, Gd3N, C2SC4, m it is the number of particles and can have a value between 1 and 5; And n is the carbon number of the fulerene, preferably it has the values 60 sns 84. On the other hand, the functionalized fulerenes can be, for example, PCBM-C60 ([6,6] -phenyl-C61-methylbutyrate) PCBM- C70 ([6,6] -phenyl-C71-methylbutyrate).
    In a preferred embodiment, the counterion (X) of the nanocapsule is selected from CF, SO "CF, COi, cr, Br", CIO, -, PF, -, SbF, -, BFi, NO, -, BPh, -, 50 / -, PO, '· or BARF. More preferably X is CF3S03 ·, BARF- or any of its combinations; where Ph is phenyl and BARF-is [B [3,5- (CF3hC6H3J4l. The number of counterions to be used will be adequate to compensate for the octacathionic charge of the nanocapsule, for example, in the case of being monoanionic the total number of counterions for Neutralizing the nanocapsule is eight, four if they are dianionic, or any possible combination thereof.
    In another preferred embodiment, each R1 independently represents hydrogen
    or fluorine, preferably all R1 of the nanocapsule are hydrogen.
    In another preferred embodiment, each R2 independently represents a
    hydrogen or a (C, -C4) alkyl group, even more preferably all R2 of the
    Nanocapsule are methyl.
    In another preferred embodiment, each RJ independently represents a hydrogen or a (C, -C4) alkyl group, more preferably all RJ of the nanocapsule are methyl.
    In another preferred embodiment, each R4 independently represents hydrogen 10 or fluorine, preferably all R4 of the nanocapsule are hydrogen.
    In another preferred embodiment, M is Pd or Cu and M 'is Zn or Pd.
    In another preferred embodiment, R is hydrogen, R2 and Rs are methyl, ~ 15 is Pd, M 'is Zn, n is 2 and X is CF, SOi or BARF',
    In another preferred embodiment, R is hydrogen, R2 and Rs are methyl, ~ is Cu, M 'is Pd, n is 2 and X is CFJSOJ ·.
    it's hydrogen, M
    it's hydrogen, M
    Another aspect of the present invention relates to the use of the nanocapsule of the present invention, for the separation and / or purification of fulerenes.
    When n is 2 in the metal macrocyclic compounds of general formula (11), the nanocapsule is useful for the separation and / or purification of size puffers between
    25 C60 and C84, both included. When n is 1 in the metal macrocyclic compounds of general formula (11), the nanocapsule is useful for the separation and / or purification of fulerenes of a size smaller than C60. and when n is 3 in the metal macrocyclic compounds of general formula (11), the nanocapsule is useful for the separation and / or purification of fulerenes of a size greater than C84.
    Another aspect of the present invention relates to the possibility of encapsulating the various liquid phase fulerenes (mixture of solvents where nanocapsule and fulerenes are dissolved), or alternatively with one of the solid phase components. For example, suspension of the nanocapsule (solid state) in solution of
    35 fulerenes in, for example, toluene, or suspension of fulerenes (solid state) in nanocapsule solution in, for example, acetonitrile.
    The present invention demonstrates the ability of nanocapsules to encapsulate fulerenes of different sizes. It has been demonstrated by high resolution mass spectrometry and, in some cases, by X-ray crystallography the encapsulation of C60, C70, C76, C78, C84 from mixtures of sooty soles
    5 ("Fullerene extract": purchased at SES Research, with a ceo content of 70%, C70 of 28%, higher fullerenes of 2%. "Fullerene soot": Aldrich, ceo is 5.32%, the C70 of 1.54 %, and that of higher fullerens (> C70) less than 0.14%)
    Therefore, yet another aspect of the present invention relates to a method of
    10 encapsulation of rubber bellows of size between C60 and C84, both included, comprising the following steps:
    to. dissolving a nanocapsule formed by two parallel (metal) tetracarboxylated porphyrins of the general formula (1) joined by four metal macrocyclic compounds of the general formula (11) through a
    15 M-carboxylate bond, and against ions (x) in a suitable number to compensate for the octacathic charge of the nanocapsule:
    or
    "I" ",) (" I "" ')
    (R #R R, #R,
    ,, n n M
    , / I ~
    ,, ,! l /! ~ ""
    or
    20 (1) (11)
    where: M 'is selected from the list comprising 2H, Zn, Pd, Cu, FeCl, Ir,PI, Ag, AuCI, Ni, Ru, Al, Pb, SnCI "InCI, SbCI, TiO, ZrCI" CrCI, goes;M, R1, R2 • R3 and R4 are defined above and n is 2;
    with a solvent selected from acetonitrile, CH2Cb, acetone, methanol or any combination thereof;
    b. add the dissolved nanocapsules from step (a) or the nanocapsules withoutdissolve, leaving the nanocapsules in suspension, to the fulerenes5 dissolved in toluene, 1,2-dichlorobenzene, carbon disulfide or anyof their combinations; or
    b '. alternatively to step (b) add to the dissolved nanocapsules in step (a) the solid-state, undissolved, the fulerenes, with said fulerenes being suspended;
    10 where the proportion of the solvent of the fulerene of step (b) / solvent of the nanocapsule of step (a) is between 9/1 to 4/1 and the temperature at which the above steps are carried out is between 0 ° C and 50 ° C, preferably the temperature is 20-30 ° C, and more preferably 25 ° C.
    In a preferred embodiment of the encapsulation method, the dissolved nanocapsules of step (a) are added to the dissolved fulerenes, that is to say in a liquid state.
    In another preferred embodiment, the rubber steels to be encapsulated are selected from C60, C70, C76, C78, C84 or any of their mixtures.
    In a more preferred embodiment the proportion of the solvent of the fulerene of step (b) / solvent of the nanocapsule of step (a) is 4/1. More preferably the solvent of step (a) is acetonitrile, and / or the solvent of step (b) is toluene.
    In a preferred embodiment of the encapsulation method of the present invention, M 'is Zn, M is Pd, R1Y ~ are H, R2Y R3 is methyl and X is BARF of the nanocapsule of step (a).
    In another preferred embodiment of the encapsulation method of the present invention, 30 M 'is Pd, M is Cu, R1 and ~ are H, Rz and R3 are methyl and X is CF3S03 of the nanocapsule of step (a).
    After the encapsulation, and secondly, the extraction of the encapsulated fulerenes is carried out exclusively with washes of the host system35 in solid state with different solvents, whereby the frelerenes released are obtained directly in solution while the remaining solid residue consists
    mostly in empty nanocapsule, which is prepared without any additional operation for another encapsulation cycle. The recycling process has been shown to be effective using an encapsulated C60 sample, and has been tested up to 5 times so that the integrity of the nanocapsule is not affected.
    Therefore, another aspect of the present invention relates to the controlled release of encapsulated fulerenes.
    A preferred embodiment relates to a method for the separation of C60 from a mixture of fulerenes, comprising:
    to. encapsulating said fulerenes by the encapsulation method of the invention described above; Y
    b. wash three times (preferably a minimum of approximately 0.3 mL per wash) encapsulated fulerenes of step (a) with a mixture
    15 of 1,2-dichlorobenzene: CS2 in a ratio of 1: 1 to 0: 1 and where the encapsulated fulerenes are supported on a filtration column (preferably celite ®).
    In another preferred embodiment with mixtures of C60 and C70, the
    Selective release with washing of the host-host compound in solid phase with organic solvents of different polarity.
    More preferably, a method for selectively and sequentially separating C60 and C70 from a mixture of rubber blades comprises separating the C60 size fulerene.
    25 by steps (a) and (b) of the method described above, in this way C60 (dissolved in the solvent mixture) is fully released while C70 remains encapsulated and in a solid state; Y
    C. The precipitate obtained in step (b) is suspended in toluene and treated with triflic acid. The C70 dissolves in the middle and recovers
    30 in full and the remaining solid can be treated for the recovery of the nanocapsules and their reuse.
    Another aspect of the present invention relates to the recycling of the nanocapsule, since once the washes have been performed for the extraction of the encapsulated fulerene, the nanocapsule can be reused after at least 5 cycles of extraction by washing.
    Therefore, the above-described methods of encapsulation and separation of ceo and, optionally of C70, may comprise an additional step in which the solid comprising the nanocapsule and fulerene is dried and NEt is added) (It is ethyl) and subsequently it dissolves with CH) CN, and in this way the nanocapsule is recovered for later use.
    Therefore, it has been shown that the nanocapsule family of the present invention has a very high affinity for encapsulation of fulerenes and that a methodology for selective extraction has been developed with the possibility of reusing the nanocapsule for additional extraction cycles.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    Fig. 1: Graphical representation of the nanocapsules of the invention. (a) represents the compound of the general formula (1) (3) and the compound of the general formula (11) (2) without the metals M; (b) represents the synthesis of two compounds of the general formula (1) (3) with four compounds of the general formula (I) (1-2), to form the nanocapsule (4); (c) represents a structural scheme of a nanocapsule where n is 2.
    Fig. 2: High-resolution ESI-MS mass spectrometry analysis of the precipitate obtained after five cycles of extraction of the C60 @ 5 'sample (BARF), by washing with 1,2-dichlorobenzene: CS, (1 :one).
    Fig. 3: ESI-MS of the mixture formed after adding fullerene soot to the nanocapsule S · (BARF) 8
    Fig. 4: Analysis by ESI-MS showing the highest affinity of C70 with respect to ceo (10 times higher).
    5 Fig. 5: Differential separation of fulerenes according to the excess of "fullerene extract" with respect to the capsule 5 (BARF) a. Enrichment of C84 using large excesses of "fullerene extract".
    EXAMPLES
    1O Example 1: Synthesis of the nanocáosulas of the invention
    15 20 Sinlesis of the Me2pp ligand (and its S2pp and H2pp) S2pp: 1.02 9 of biphenyl 4,4'-dicarbbaldehyde (0.48 mmol) are dissolved in 200 ml of THF. Another solution of 0.51 g of diethylenetriamine (0.49 mmol) in 100 ml of THF is prepared. Using a compensated addition funnel, the dialdehyde solution is added dropwise to the diethylenetriamine solution. The mixture was stirred for 10 h. The formation of a white powder is observed, and the solid is filtered off. (Yield: 64.6%). lH_ NMR (400 MHz, cac !,) O ppm: 8.31 (s, 4H, N = CH), 7.56-7.54 (d, J = 8.32 Hz, 8H, arom), 7, 41-7, 38 (d, J = 8.32 Hz, 8H, arom), 3.80-3.78 (m, 8H, CH,), 3.00-2.98 (m, 8H, CH, ), 2.14 (s, 2H, NH). FT-IR v (cm- '): 1372 (CN 51), 1643 (C = N st), 1650-2000, 2879, 2945 (CH st, sp'), 3027 (= CH st), 3062 (arC- H st), 3300 (NH st). ESI-MS (miz): 555, 3 "S2pp + (W)}), 281.7 ({S2pp + (W),).
    "'" N NH NV // L / J
    H2pp: 0.55 g of S2pp (0.99 mmol) was added to a 250 ml flask and dissolved with 50 absolute ethanol. Then 0.237 g of NaBH4 (13.22 mmol) are added slowly. The reaction mixture was stirred for 16 h, 5 ml of 1M HCI was added, and the solution was stirred an additional 45 minutes. After this time, the ethanol was removed under reduced pressure, and 20 ml of water is added to the reaction mixture. The H2pp product, which remains in the aqueous phase, is extracted with CH) CI (3x25 ml). The organic phases are mixed, dried with anhydrous MgSO4 and filtered. Finally the solution is dried under vacuum pressure. The product was obtained as a solid
    White. (Yield: 78.1%). 'H-NMR (400 MHz, CDCI,) ~ ppm: 7.48-7.46 (d, J =
    10 8.24 Hz, 8H, arom), 7.36-7.34 (d, J = 8.20 Hz, 8H, arom), 3.8 (s, 8H, CH,), 2.90-2 , 82 (m, 16H, CH,), 1.68 (broad band, NH). FT-IR v (cm ''): 1103 (C-N st), 1496, 1437 (CH, 0), 1650-2000,2876,2922 (C-H st, sp '), 3294 (NH st). 0 ~ /)
    ""
    NH N HN
    " l / J
    Me2pp: 0.66 g of H2pp (1.2 mmol) was added to a 100 ml flask and mixed with 10 ml of formaldehyde, 8 ml of formic acid and 10 ml of water. The resulting mixture is heated at reflux for 12 h. After this time, the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. Then 25 ml of 30% NaOH are added. The product was extracted with CHCh (3x25 ml). The organic phases were combined, dried with anhydrous MgSO4 and filtered. The remaining solution is dried under vacuum pressure, and the product obtained is purified by recrystallization with acetone. (Yield: 39.6%). lH-NMR (400 MHz, CDCI,) oppm: 7.39 (d, J = 8.24 Hz, 8H, arom), 7.29 (d, J = 8.24 Hz, 8H,
    25 arom), 3.47 (d, J = 20.06 Hz, 8H, CH,), 2.57-2.49 (m, 16H, CH,), 2.28 (s, 6H, CH,) , 2.22 "s, 12H, CH,). FT-IR v (cm "): 1462 (CN st), 1650-2000, 2780 (CH st, sp '), 2935 (arC-H st), 2967 (CH st, sp'). ESI-MS (miz ): 647.4 «Me2pp + Hn
    Molecular Clip (Pd-1) (FRAGMENT 1-2 of Fig. 1 with M = Pd). Pd-1 (AcO),
    5 (where AcO is acetate) In a 0.03 g round bottom flask of Me2pp ligand
    (0.05 mmol), 0.021 9 of Pd (AcO), (0.1 mmol) and 10 ml of GH, anhydrous GN is
    mixed. The mixture is heated at reflux temperature, under nitrogen atmosphere, for 18 h. The solvent of the solution obtained is concentrated to a volume of 2 ml, under reduced pressure, filtered through Celite® and recrystallized by slow diffusion of diethyl ether. [Pd 2 (Me2pp) (AcOh] (AcOh is obtained as a yellow crystalline solid. (Yield: 81.7%). 1H-NMR (400 MHz, CD3CN) ) Ppm:
    8.37 (d, J = 8 Hz, 9.3 H, arom), 8.15 (d, J = 8 Hz, 8 H, arom), 7.94 (d, J = 8 Hz, 1.3 H, arom), 4.06 (d, J = 13 Hz, 5.1 H, -GH, -), 3.68 (m, 4.8 H, -GH, -), 3.34 (s, 12 H, N-GH,),
    3.31 (s, 2.2 H, N-GH,), 3.25 (m, 4.8 H, -GH, -), 3.11 (d, J = 13 Hz, 4.8 H, -GH, -), 2.38 (d, 15 J = 14 Hz, 4.7 H, -CH, -), 2.30 (d, 4.8H, -CH, -), 2.07 (s, 6 H, AcO), 2.05 (s, 0.9H, AcO),
    1.70 (s, 7.2 H, AcO), 1.50 (s, 0.9 H, N-CH3), 1.41 (S, 6 H, N-CH,). ESI-MS (miz): 1307.3 (([Pd, (Me2pp) (AcO) 'J (AcO),} »), 489.1 (([Pd, (Me2pp) (AcO) &' O).
    2 (OAc)
    Pd-1 · (AcO), (CF3S03),: Pd-1 · (AcO), (CF3S03h is obtained from Pd-1 · (AcO) .. 0.04 9 of Pd-1 · (AcO) 4 (0.04 mmol) was dissolved in 25 ml of CH) CN. An excess is added
    5 NaCF) S03 (1 to 4.2 equivalents) and the mixture was stirred vigorously for 6 h. The reaction mixture was concentrated to a volume of 2-3 ml under reduced pressure, filtered through Celite® and recrystallized by slow diffusion of diethyl ether. A yellow crystalline solid is obtained. (Yield: 90.1%).
    10 Molecular Clip (Cu-1) (FRAGMENT 1-2 of Fig. 1 with M = Cu). Cu-1 · (CF3S03) .: to a suspension of Me2pp ligand in CH) CN (40 mg, 0.06 mmol, 1.5 ml), a solution of Cu (CF3S03h in CH3CN (45.0 mg,) was added 0.12 mmol, 1 ml.) After stirring for 30 minutes, the solution was filtered through Celite® and recrystallized by diffusion of diethyl ether. A dark red crystalline solid was obtained (yield:
    15 94.7%). ESI-MS (miz): 1221.2 ({(Cu-1) '(CF3S03),) "), 535.0 ({(Cu-1)' (CF3S03),)"), 307.7 ({(Cu-1) - (CF3S0 3).) 3 '). --V'II'Í /
    '-..--'
    'r
    ~ O) 5Cf) I ~
    Do you
    Synthesis of molecular nanocapsule 4 · (CF3S03) S. (Fig 1, where M = Cu and M '= Pd, which consists of two (metallo) porphillins of formula (1) where all ~ are hydrogen
    5 and M 'is Pd linked to four macrocycles of formula (11) (Cu-1 above) via M-carboxylate bonds and eight CF3S03 counterions) To a suspension of 5,10, 15,20-tetrakis (4-carboxyphenyl) ) -porphyrin-Pd "in DMF (6.53 mg, 0.029 mmol, 1 mL) a solution of triethylamine in DMF (4 IJL in 0.5 mL) was added. Simultaneously, molecular clip Cu-1 dissolved in DMF ( 20 mg, 0.014
    10 mmol, 1.5 mL) and added dropwise to the metalloporphyrin solution. After stirring overnight the solution was filtered through Celite® and recrystallized by ether diffusion. A dark red crystalline solid was obtained (yield: 62.9%). ESI-MS (miz): 2886.4 «4 '(CF, SO,) sl"), 1875.9 «4' (CF, SO ') 5}"), 1368.4 «4' (CF, SO,),}") , 1064.8 «4 '(CF, SO, h} 5'), 862.9« 4 '(CF, SO,),) "), 718.3
    15 «4 '(CF, SO,)} 7'), 609.9« 4) ").
    Synthesis of molecular capsule 5 · (CF3S03) s. (Fig. 1 nanocapsule where M = Pd and M '= Zn, consisting of two (metallo) porphillins of formula (1) where all R4 are hydrogen and M' is Zn joined by four macrocycles of formula (11) (Pd -1 above) and
    20 eight counterions CF3S03) 5 · (CF3S03) s: 10.56 mg of 5.10, 15.20-tetrakis (4-carboxyphenyl) -porphyrin-Zn "(2, 0.01 mmol) were weighed in a flask of 10 mL, then 1 mL of DMF is added, 10 1-11 of triethylenetriamine dissolved in 0.5 ml of DMF are added to the metalloporphyrin solution, finally 30 mg of Pd-1 (AcOh (CF3S03h (0.02 mmol) complex
    25 dissolved in 2.5 ml of DMF are added to the mixture. The solution obtained is heated at 105 ° C under reflux for 16 h. After the reaction time, the mixture is
    cooled to room temperature, filtered through Celite © and recrystallized by
    diffusion of diethyl ether. (Yield: 67.1%). 'H-NMR (400 MHz, CD, CN) or ppm: 8.60 (dd, 8 H, arom-porph), 8.58 (s, 16H, pyrrote rin9), 8.35 (dd, J = 8 Hz, 8H, arom- porph),
    8.30 (d, J = 8.5 Hz, 32 H, arom-clip), 8.15 (d, J = 8.5 Hz, 32 H, arom-clip), 8.10 (dd, J = 8 Hz, 8H, arom-porph), 7.98 (dd, J = 8 Hz, 8H, arom-porph), 4.07 (d, J = 13 Hz, 16 H, CH, -), 3.70 (m, 16H, -CH, -), 3.60 (s, 48 H, N-CH,), 3.38 (m, 16 H, -CH, -), 3.15 (d, J = 13 Hz, 16 H, -CH, -), 2.49 (dd, J = 13.5, 16 H, -CH, -), 2.39 (dd, J = 13.5, 16 H, -CH, -),
    1.58 (s,24HN-CH,)ESI-MS(m iz):1433.5 «5 ·« CF, SO,),),} '»,1117.3
    ({5 '(CF, SO,),}' », 906.7({5 · (CF, SO,),} '»,755.5({5 · (CF, SO,) I '»,642.2
    «(3 · (CF, SO,)) '».
    Synthesis of molecular capsule 5 · (BARF) 8. (Fig. 1 nanocapsule where M = Pd and M '= Zn, which consists of two (metallo) porphillins of formmu la (1) where all R, are hydrogen and M' is Zn joined by four macrocycles of formula (11 ) (Pd-1 above) and eight counterions BAR F ') 5 · (BARF) 8: 0.02 g of 5- (CF3S03) 8 (3.2 J. lmoles) dissolve in 10 ml of CH2CI2. An excess of NaBArF salt (1 to 10 equivalents) is added and the mixture is stirred vigorously for 16 h. The reaction mixture is filtered and the product is obtained by precipitation with diethyl ether. The purple powder was washed several times with diethyl ether to remove excess NaBArF. (Yield: 38%). lH-NMR (400
    MHz, CD, CN) or ppm: 8.60 (dd, 8 H, arom-porph), 8.58 (s, 16H, pyrrole rin9), 8.35 (dd, J = 8 Hz, 8H, arom-porph), 8.30 (d , J = 8.5 Hz, 32 H, arom-clip), 8.15 (d, J = 8.5 Hz, 32 H, arom-clip), 8.10 (dd, J = 8 Hz, 8H, arom-porph), 7.98 (dd , J = 8 Hz, 8H, arom-porph),
    7.68 (m, 96 H, NaBARF), 4.07 (d, J = 13 Hz, 16 H, -CH, -), 3.70 (m, 16H, -CH, -), 3.60 (5, 48 H, N-eH ,), 3.38 (m, 16 H, -CH, -), 3.15 (d, J = 13 Hz, 16 H, -CH, -), 2.49 (dd, J = 13.5, 16 H, -CH, -) , 2.39 (dd, J = 13.5, 16 H, -CH, -), 1.58 (s, 24 H, N-CH,). ESI-MS (miz): 2147.99 ({5 '(BARF),}' », 1545.74 ({5 '(BARF),}'», 1144.24 ({5 '(BARF),}' », 857.48 ({5 '(BARF)}' », 642.42 ({5 · (BARF)} '».
    The characterization of the hostless nanocapsules was performed by high resolution mass spectrometry (HR-ESI-MS), by X-ray diffraction and by NMR studies and infrared FT-IR spectroscopy.
    Example 2: Encapsulation and Release of Fulerenes using nanocapsules
    The prismatic tetragonal nanocapsule (5 · (BARFls) is capable of encapsulating fulerenes of different sizes, mainly Cso, C70, C7S, C7S and CS4 'The encapsulation is performed by mixing the dissolved box in acetonitrile and equimolar amounts of fulerenes dissolved in toluene ( 25 ° C, acetonitrile: toluene 1: 4) Alternatively, encapsulation is also effective by suspending 5 '(BARF) s in a solid state within a tollene solution in toluene, or by also suspending fullerene in an S' solution (BARF ) s in acetonitrile In addition, these fulerenes can be released from the interior of the nanocavity by washing with different organic solvents This extraction is quick and simple, and is based on the difference in solubility of the fulerenes and the nanocapsule. nanobox with a solvent in which the fulerenes are highly soluble but the nanocapsule is not, we get it to remain in suspension and only solubilize the f Ulerenos The solution
    15 containing the fulerenes is separated by filtration of the solid and finally the extracted fulerenes are precipitated by the addition of acetonitrile, and separated by centrifugation.
    Preparation of Cso @ S '(BARF) s_ 2.5 mg of nanocapsule S' (BARF) s (0.2 ~ lmoles, 1
    20 equiv.) Were dissolved in 100 IJI of CH 3CN. Then 1 equiv. de Cso was added along with 400 IJI of toluene. The mixture was stirred at room temperature for 5 minutes. After the reaction time, the mixture is filtered through cotton and recrystallized by diffusion of diethyl ether. 'H-NMR (400 MHz, CD, CN) 1i ppm: 8.64 (dd, 8 H, arom-porph), 8.55 (s, 16H, pyrrole ring), 8.35 (dd, J = 8 Hz, 8H, arom- porph), 8.30
    25 (d, J = 8.5 Hz, 32 H, arom-clip), 8.14 (d, J = 8.5 Hz, 32 H, arom-clip), 8.04 (dd, J = 8 Hz, 8H, arom-porph), 7.99 (dd, J = 8 Hz, 8H, arom-porph), 7.68 (m, 96 H, NaBARF), 4.07 (d, J = 13 Hz, 16 H, -CH, -), 3.70 (m, 16H, -CH, -), 3.60 (s, 48 H, N-CH,), 3.38 (m, 16 H, -CH, -), 3.15 (d, J = 13 Hz, 16 H, -CH, -), 2.49 (dd, J = 13.5, 16 H, -CH, -), 2.39 (dd, J = 13.5, 16 H, -CH, -), 1.58 (s, 24 H, N-CH,). ESI-MS (miz): 2328.14 30 «C", @ 5 '(BARF),) "), 1689.89« C ,, @ 5' (BARF),) "), 1264.40 ({C ,, @ 5 '(BARF),)"),
    960.48 ({C ,, @ 5 '(BARF)} "), 732.54 ({C ,, @ 5 · (BARF)}").
    Preparation of C70 @ 5 '(BARF) s. 2.5 mg of nanocapsule 5 '(BARF) s (0.2 ~ moles, 1 equiv.) Were dissolved in 100 IJI of CH 3CN. Then 1 equiv. of C70, 35 was added along with 400 IJI of toluene. The mixture was stirred at room temperature for 5 minutes. After the reaction time, the mixture is filtered through cotton and
    recrystallized by diffusion of diethyl ether. 'H-NMR (400 MHz, CD, CN) 1i ppm: 8.66 (dd, 8
    H, arom-porph), 8.48 (s, 16H, pyrrole ring), 8.33 (d, J = 8.5 Hz, 32 H, arom-clip), 8.14
    (d, J = 8.5 Hz, 32 H, arom-clip), 8.00 (m, 8H, arom-porph), 7.68 (m, 96 H, NaBARF), 4.07 (d, J = 13 Hz, 16 H, -CH, -), 3.70 (m, 16H, -CH, -), 3.60 (s, 48 H, N-CH,), 3.38 (m,
    5 16 H, -CH, -), 3.15 (d, J = 13 Hz, 16 H, -CH, -), 2.49 (dd, J = 13.5, 16 H, -CH, -), 2.39 (dd, J = 13.5, 16 H, -CH, -), 1.58 (s, 24 H, N-CH,). ESI-MS (miz): 2358.19 «C ,, @ 5 '(BARF),)"), 1713.97 «C ,, @ 5' (BARF),) 5 '), 1284.42 ({C ,, @ 5' ( BARF),) "), 977.62 ({C ,, @ 5 '(BARF)} 7'), 747.53 ({C ,, @ 5 · (BARF)} 8 ').
    The release of the C60 fulerene from inside the nanocapsule from a pure sample of CeO-nanocapsule complex is performed by loading the sample (10 mg) of C6o @ S- (BARF) into a solid state on a column using Celite as a solid filter support. ®. Three consecutive 1 mL washes of the 1,2-dichlorobenzene / CS2 (1: 1) mixture completely release the inside of the capsule, leaving all the C60 in the filtrate and
    15 empty capsule in solid state S- (BARF) 8 loaded in the column. Analysis of the solid sample remaining in the column by HRMS certifies that it consists of an empty box in a purity> 95%. Then the S- (BARF) 8 capsule loaded in the column is redissolved in CH3CN and reloaded with C60 dissolved in toluene (CH3CN / 1/4 toluene mixture). Once loaded with C60, compound C60 @ S- (BARF) g is
    20 precipitates with diethyl ether and reloads on the same chromatography column (celite® as solid support) used for the first wash. The same procedure is repeated up to 5 times and the integrity of S- (BARF) g is certified by HRMS after each wash. At the end of the 5 cycles, more than 54% of S- (BARF) g is recovered. The cash losses observed are mainly due to the process
    S-solution (BARF) s once emptied of C60 and precipitation of CeO @ S- (BARF) g with diethyl ether, and not the decomposition of the compound. It is thus shown that the box works like a recyclable sponge. (Fig. 2)
    The nanocapsule S- (BARF) 8 is capable of encapsulating the different fulerenes present
    30 in the soot resulting from the production of fulerenes (fullerene extract), from C60 to C84. The encapsulation of fulerenes has been tested with "fullerene extract" (purchased from SES Research, with a content of C60 70%, C70 28%, large fulerene (higher fullerenes) 2%). Using a ratio of 1: 3 by weight of nanocapsule S- (BARF) a and commercial "fullerene soot" (Aldrich) (C60 is 5.32%, that of C70 of the
    35 1.54%, and that of "higher fullerenes" (> C70) less than 0.14%, the rest being amorphous carbon, carbon nanotubes and graphite, for which the nanocapsule is totally
    ineffective), it is capable of encapsulating C60, C70, C74, C76 and C84 exclusively, as determined by high resolution mass spectrometry. (Fig. 3)
    The encapsulation of the fulerenes at room temperature is quantitative
    5 (stoichiometry 1: 1) in seconds and at room temperature. Your encapsulation hasverified by high resolution mass spectrometry, by NMR studies (thenanocapsule and its adduct with encapsulated fulerene are diamagnetic) andFT-IR spectroscopy. The encapsulation of C60 and C70 has also been tested.through preliminary studies of X-rays with synchrotron light.
    The higher proportion of C70 than of encapsulated C60 when its concentration is 4 times lower, clearly suggests a higher affinity for C70. The same reasoning can be done in relation to C84, e76 and C72, since their percentages are extremely small in the "fullerene extract" and yet they are observed
    15 clearly as encapsulated in Fig. 3 It has been determined by HRMS that the affinity of C70 is 10 times higher than that of C60 (Fig 4).
    If it has not been possible to calculate due to the lack of availability of pure sample ofC72, C76 and C84, it is reasoned that these fulerenos have even greater affinity than the C70.
    20 This allows us a differentiated separation of fulerenes according to the excess of "fullerene extract" with respect to the S- (BARF} g capsule. Thus it is clearly observed that when the S- (BARF) s: "fullerene extract" ratio in weight it is 1: 3 basically C60 and C70 are encapsulated, while with large excesses (ratios of 1/300) very little amount of C60 is encapsulated in relation to C70, and also
    25 notes that clearly the C70 / C84 ratio decreases, indicating an enrichment of C84 as a fulerene with greater affinity (Fig. 5).
    The release of the encapsulated fulerenes mixture (in the experiment where the S- (BARF) g: "fullerene extract by weight ratio is 1: 3) is performed as follows: 5 mg of the nanocapsule with fulerenes, fulerenes @ S- (BARF) s, is loaded in a solid state on a column with celite® as a solid support, and 3 washes of 1 mL of the 1,2-dichlorobenzene: CS2 1: 1 mixture are performed, allowing the C60 to be released exclusively in a pure way, leaving on the column the solid residue consisting of empty capsule S- (BARF} g and capsule with fulerenes equal to or greater than
    35 C70. Later washed with CS2 exclusively allow to extract up to 10% of the C70 encapsulated in a pure way.
    The release of the rest of higher fullerenes can be done in two ways: a) the use of excess triflic acid (CFJSOJH, 20 equivalents with respect to the capsule) added on a suspension of fulerenos @ S- (BARF) s (where the C60 has been previously released) at room temperature leads to irreversible disassembly of the
    5 nanocapsule and immediate release of the mixture of fulerenes; b) the use of 3 equivalents of CFJSOJH allows to extract the fulerenes equal or larger than C70, due to a destabilization of the capsule without disassembling it. The addition of 3 eq of NEh (triethylamine) as a base to neutralize the triflic acid used is essential to recover the capsule completely (HRMS certified).
    10 These tests show that the developed nanocapsule is capable of modeling the dimension of its interior space to accommodate guests of different sizes (from C60 to C84), thanks to the torsion capacity at the level of the eight metal-carboxylate coordination bonds and the slight flexibility inherent in the substructure
    Porphyrinic 15
    权利要求:
    Claims (26)
    [1]
    1. Nanocapsule formed by two parallel (metallo) tetracarboxylated porphyrins of
    general formula (1) linked by four metal macrocyclic compounds of5 general formula (11) through an M-carboxylate bond, and against ions (X):
    or
    ",
    , ""
    'R,
    ,
    ,,,
     ,, '
    % "" "" or 'R, ~ 0t / j / R'
     ',, -'
    "~ M-- ~ R) ~ R)
    (:: 1 # R, or e, I # R,
    or
     ,, M
    '" ,/one"---, ,
     or R! l / !; U "R '
    or
    (1) (11) 10
    where: M 'is selected from the list comprising 2H, Zn, Pd, Cu, FeCI, Ir, Pt, Ag,AuCI, Ni, Ru, Al, Pb, SnCI "InCI, SbCI, TiO, ZrCI" CrCI, VD;M is a metal that is selected from the list comprising Pd, Cu, Pt, Ni and Zn;each R1 and each ~ independently represent a hydrogen or a
    15 halogen; each R2 and each R3 independently represent a hydrogen or an alkyl group (C, -C,);
    n has a value between 1 and 3.
    2. A nanocapsule according to claim 1, wherein M 'can be selected from the list comprising 2H, Zn, Cu, FeCI, Ir, PI, Ag, AuCI, Ni, Ru, Al, Pb, SnCI "InCI, SbCI, TiO, ZrCI "CrCI, VD.
    [3]
    3. Nanocapsule according to any one of claims 1 or 2, wherein n is 2 or 3. 25
    [4]
    4. Nanocapsule according to any of claims 1 to 3, wherein X is
    select from CF3 S03-, CF3C02-, cr, Sr ", CI04-, PF6-, SbF6-, SF4-, NOJ-, BPh43
    , sun or, P04-or SARF-.
    5 5 Nanocapsule according to any one of claims 1 to 4, wherein X is CF3S03
    or BARF-and said nanocapsule is formed by eight against ions_
    [6]
    6. Nanocapsule according to any one of claims 1 to 5, wherein each R1 independently represents hydrogen or fluorine.
    [7]
    7. Nanocapsule according to any one of claims 1 to 6, wherein all R1 are hydrogen.
    [8]
    8. Nanocapsule according to any one of claims 1 to 7, wherein each R2 independently represents a hydrogen or a (C, -C4) alkyl group.
    [9]
    9. Nanocapsule according to any of claims 1 to 8, wherein all R2 are methyl_
    10. Nanocapsule according to any one of claims 1 to 9, wherein each R3 independently represents a hydrogen or a (C1-C4) alkyl group.
    [11]
    11. Nanocapsule according to any of claims 1 to 10, wherein all R3 are methyl.
    [12]
    12. Nanocapsule according to any of claims 1 to 11, wherein each R4 independently represents hydrogen or fluorine.
    13 Nanocapsule according to any one of claims 1 to 12, wherein all R 4 30 are hydrogen.
    [14]
    14. Nanocapsule according to any one of claims 1 to 13, wherein M is Pd or Cu and M 'is Zn or Pd.
    [15]
    fifteen. Nanocapsule according to any one of claims 1 to 14, wherein n is 2.
    [16]
    16. Nanocapsule according to any one of claims 1 to 15, wherein R1 is hydrogen, R2 and RJ are methyl, R4 is hydrogen, M is Pd, M 'is Zn, n is 2 and X is CF3S03' or BARF.
    17. Nanocapsule according to any one of claims 1 to 15, wherein Rj is hydrogen, R2 and RJ are methyl, ~ is hydrogen, M is Cu, M 'is Pd, n is 2 and X is CFJSOJ-.
    [18]
    18. Use of the nanocapsule according to any of claims 1 to 17, for the separation and / or purification of fulerenes.
    [19]
    19. Use of the nanocapsule according to any of claims 1 to 17, for the separation and / or purification of fulerenes of size between C60 and C84, both included, when n is 2.
    [20]
    twenty. Use of the nanocapsule according to any of claims 1 to 14, for the separation and / or purification of fulerenes of a size smaller than C60, when n is
    one.
    Use of the nanocapsule according to any one of claims 1 to 14, for the separation and / or purification of fulerenes of a size greater than C84, when n is
    [3]
    3.
    [22]
    22. Encapsulation method of rubber bellows of size between C60 and C84, both included. which includes the following steps:
    to. dissolve a nanocapsule formed by two parallel tetracarboxylated (metallo) porphyrins of the general formula (1) joined by four metal macrocyclic compounds of the general formula (11) through the M-carboxylate bond, and counterions (X):
    or
     R'I ~ R) (R'I ~ R)
    (R, # R, R, # 'R,
    ""
    / r ~
    N N N
     or · R / V!; U'R,
    or
    (1) (11)
    wherein: M ', M, R1, R2, R3 and R4 are defined in claims 1 to 17;
    5 and n is 2;with a solvent selected from among acetonitrile, CH2CI2, acetone,methanol or any combination thereof; Y
    b. add the dissolved nanocapsules from step (a) or the undissolved nanocapsules to the fulerenes dissolved in toluene, 1,2-dichlorobenzene, carbon disufide or any combination thereof; or b '. add to the nanocapsules dissolved in step (a) to the fulerenes in state
    solid, undissolved; where the proportion of the solvent of the fulerene of step (b) / solvent of the nanocapsule of step (a) is between 9/1 to 4/1 and the temperature at which they are carried
    15 The above steps are between 0 ° C and 50 ° C.
    [23]
    23. Method according to claim 22, wherein the rubber steels to be encapsulated are selected from C60, C70, C76, C78, C84 or any of their mixtures.
    A method according to any one of claims 22 or 23, wherein the solvent of step (a) is acetonitrile.
    [25]
    25. Method according to any of claims 22 to 24, wherein the solvent of step (b) is toluene.
    [26]
    26. Method according to any of claims 22 to 25, wherein the proportion of the solvent of the fulerene of step (b) / nanocapsule solvent of step (a) is 4/1.
    [27]
    27. Method according to any of claims 22 to 26, wherein the temperature is 20-30 ° C, preferably 25 ° C.
    [28]
    28. Method according to any of claims 22 to 27, wherein M 'is Zn, M is Pd, R, Y ~ are H, R2 and R3 are methyl and X is BARF-of the nanocapsule of the passage
    (to)
    [29]
    29. Method according to any of claims 22 to 27, wherein M 'is Pd, M is Cu, R, and ~ are H, R2 and R3 are methyl and X is CF3S03-of the nanocapsule of step (a).
    [30]
    30 Method for the separation of C60 from a mixture of fulerenes, comprising:
    to. encapsulating said fulerenes by the method described in claims 22 to 29; Y
    b. wash the encapsulated fulerenes of step (a) three times with a mixture of 1,2-dichlorobenzene: CS2 in a ratio of 1: 1 to 0: 1 and where the encapsulated fulerenes are supported on a filtration column.
    [31]
    31. A method for the selective and sequential separation of C60 and C70 from a mixture of rubber carriers comprising: separating the C60 size fulerene by means of steps (a) and (b) of the method described in claim 30; Y
    C. The precipitate obtained in step (b) is suspended in toluene and treated with triflic acid.
    [32]
    32 Method according to any of claims 22 to 31, further comprising a step in which the solid comprising nanocapsulated fulerene is dried and NEh is added and subsequently dissolved with CH3CN for recovery of the nanocapsule.
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