GB2463046A

GB2463046A - Metal complexes comprising a fullerite

Info

Publication number: GB2463046A
Application number: GB0815743A
Authority: GB
Inventors: Richard James Curry; Lok Cee Chong; Jose Virgilio Anguita Rodrigurez; Gabriele Sabine Wagner; Sembukuttiarachilage Ravi Pradip Silva
Original assignee: University of Surrey
Current assignee: University of Surrey
Priority date: 2008-08-29
Filing date: 2008-08-29
Publication date: 2010-03-03
Also published as: GB0815743D0

Abstract

A process for the preparation of a fullerite, said process comprising the admixture of metal complex MLwL'x(wherein M is a non-group 1 metal, each L and L' is a ligand and w and x are selected from 0 to 8), a fullerene or derivative thereof, a first solvent in which the fullerene or derivative is substantially soluble and a second solvent in which the fullerene or derivative is substantially insoluble, to precipitate the fullerite. In another aspect, the use of the above process for the preparation of particles of ML'ywherein y is 0 to 9, preferably by dissolving fullerites prepared according to the above mentioned process. Additionally, fullerites and particles prepared by the above processes, to matrices incorporating said fullerites and/or- particles, and to their uses. The preferred metal is Palladium and the preferred ligand is triphenylphosphine.

Description

Novel Processes and Materials

Technical Field

The present invention is directed to a process for the preparation of a fullerite, said process comprising the admixture of a metal complex MLWL'X (wherein M is a non-group I metal, each L and L' is a ligand and w and x are selected from 0 to 8, with the proviso that 2 w + x 9), a fullerene or derivative thereof, a first solvent in which the fullerene or derivative is substantially soluble and a second solvent in which the fullerene or derivative is substantially insoluble, to precipitate the fullerite. The present invention also relates to the use of the above process for the preparation of particles of ML' wherein y is 0 to 9, preferably by dissolving fullerites prepared according to the above mentioned process. Additionally, the present invention is directed to fullerites and particles prepared by the above processes, to matrices incorporating said fullerites and/or particles, and to uses of said fullerites, particles and matrices.

Background to the Invention

In recent years fullerenes have received a rejuvenation of interest due to the demonstration of controlled fast-growth of pristine fullerene crystals often referred to as fullerites. Fullerite tubes with diameters of 200 -300 nm have been reported, grown via a template initiated dip and dry' solvent evaporation route. However, the use of a template limits the scale of this preparation.

As an alternative, a liquid/liquid interfacial precipitation (LLIP) method for the synthesis of sub-micron sized C60 whiskers and tubes has been developed. This method has subsequently been applied to the synthesis of similar structures formed from C70 and fullerene derivatives such as C6�C3H7N. An even quicker one-step method of making high purity single crystal fullerites was reported by Jin et al. (Journal of Materials Chemistry, 2006, vol. 16, pp. 3715-3720) simply by controlled drop-wise addition of a C60/toluene solution into an alcohol solvent. This method is known as fast-LLIP (FLLIP). The synthetic procedure is completed within -2 minutes and therefore represents a significant advantage over previously reported methods that typically require days or weeks. To date however the FLLIP technique has only been applied to pure C60 fullerites.

The properties of such fullerites are now the subject of intense research due to their potential for incorporation into low-cost electronic devices. Theoretical predictions and experimental results indicate that crystals formed from C60 are n-type semiconductors with direct bandgaps that can be further tailored via doping techniques. Potential electronic devices that may benefit from such materials include n-type organic transistors, optical devices, thin film organic solar cells, organic light emitting diodes and photodetectors, due to the relatively high electron mobility of C60 (-0.1 cm2V1s1). Using the FLLIP technique a large variety of structures including truly nano-sized fullerite rods, with 80 nm diameter, can easily be obtained by precise control of growth conditions (Chong et. al., Journal of Materials Chemistry, 2008, vol. 18, pp. 3319-3324). The ability to produce large quantities of such small fullerites raises the potential for their incorporation into devices to enhance a desired property.

In addition to these electronic applications the use of fullerites has the potential to significantly impact other areas by their application for instance as adsorbents, membranes and catalysts, due to their relatively high surface area to volume ratio.

There is therefore a large demand for further novel fullerites and improved processes for their preparation.

Many metals and metal complexes find application as catalysts. For instance, palladium is an industrially important catalyst, due to its unique ability to facilitate the formation of carbon-carbon bonds. There are two classifications of industrial applications of palladium catalysts. The first type includes the oxidative reactions of olefins and aromatic compounds, and oxidative carbonylation. These reactions are catalyzed by Pd(II) salts and appropriate reoxidants. The second type are reactions catalyzed by Pd(0) complexes, including reactions of organic halides and reactions via it-allylpalladium complexes. Palladium is also frequently used for the activation of hydrogen, and the palladium fullerene complex (2-C60)Pd(PPh3)2 is known to hydrogenate acetylenic alcohols under a homogenous system. In addition, during hydrogenation of dehydrolinalool to linalool using fullerene as a ligand, a 99 % selectivity has been shown. Accordingly, fullerene-complexed metals are of great interest and have many potential applications.

In addition, there is a need to generate particles of catalytic metals and metal complexes which have a very small average diameter and hence a very high surface area to volume ratio.

To date, there has been one report of the synthesis of fullerites which include fullerenes complexed to metals (Miyazawa et al., Journal of Materials Research, 2004, vol. 19(8), pp. 2410-2414). In this method, crystals comprising C60 and the platinum complex (12-C60)Pt(PPh3)2 were obtained by slow synthesis (-2 weeks) at room temperature under a fluorescent room light. The slow growth of the crystals was believed to be the result of steric hindrance due to the large size of the platinum substituents on the complexed fullerenes, the substitutents causing the average spacing between the fullerenes to increase. There is therefore a need for improved methods of synthesis of fullerites which include fullerenes complexed to metals.

Summary of the Invention

A first aspect of the present invention relates to a process for the preparation of a fullerite, said process comprising the admixture of (a) a metal complex MLWLX, wherein M is a non-group 1 metal, wherein each L and L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein w is an integer between 0 and 8 and x is an integer between 0 and 8, with the proviso that2w+x9; (b) a fullerene and/or a fullerene derivative; (c) a first solvent in which the fullerene and/or fullerene derivative is substantially soluble; and (d) a second solvent in which the fullerene and/or fullerene derivative is substantially insoluble to precipitate the fullerite.

As used herein, the term cfullerite) refers to any crystalline form comprising a fullerene and/or a fullerene derivative, or to any polymeric form comprising a fullerene and/or a fullerene derivative. Preferably the term fullerite' refers to any crystalline form comprising a fullerene and/or a fullerene derivative. More preferably the term fullerite' refers to any crystalline form comprising a fullerene.

Preferably said crystalline or polymeric form consists of at least 50 % by weight of fullerenes and/or fullerene derivatives. More preferably, said crystalline or polymeric form consists of at least 75 %, at least 90%, at least 95% or at least 99% by weight of fullerenes and/or fullerene derivatives.

The fullerenes and/or fullerene derivatives within the fullerite may be held together by any type of molecular interaction including for example ionic bonding, covalent bonding, hydrogen-bonding and/or Van-der-Waal's interactions. Preferably the fullerenes and/or fullerene derivatives within the fullerite are held together by Van-der-Waal's interactions.

As used herein the term fullerene' refers to any closed-cage structure having twenty or more carbon atoms consisting entirely of three-coordinate carbon atoms.

Representative fullerenes include C20, C32, C36, C48, C60, C62, C70, C72, C74, C76, C78, C80, C82, C84, C, C88, C90, C94, C110, C120, C140 and C380. Preferably the fullerene has 20 to 400 carbon atoms, more preferably the fullerene has 20 to 200 carbon atoms, more preferably 40 to 150 carbon atoms, most preferably 60 to 100 carbon atoms.

Preferably the fullerene has an even number of carbon atoms. Preferably the term fullerene' refers to a compound composed solely of an even number of carbon atoms which form a closed-cage fused-ring polycyclic system with twelve five-membered rings and the rest six-membered rings. Preferred fullerenes include C60, C70, C76, C78, and C84. Particularly preferred fullerenes are C60 and C70. The most preferred fullerene is C60.

As used herein the term fullerene derivative' refers to any fullerene: (a) wherein the closed-cage structure is partially or fully unsaturated; (b) wherein one or more carbon atoms within the closed-cage structure has been replaced by one or more heteroatoms, preferably selected from B, N, 0, Si, P, S or Ge; (c) wherein the closed-cage structure is functionalised with one or more groups selected from -OH, -SH, -NH2, -CN, -NO2, -0-, -5-, -NR1-or -R1, wherein each R1 is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group, and wherein optionally any two or more R1 groups together with the atom or atoms to which they are attached may form a ring; and/or (d) wherein the closed-cage structure is functionalised with one or more further fullerenes or further fullerene derivatives.

Preferred fullerene derivatives include N-methylfulleropyrrolidine (C60C3H7N); (1,2-methanofullerene C60)-61-carboxylic acid (C6OCHCO2H) and esters thereof such as tert-butyl (1,2-methanofullerene C60)-6 I -carboxylate; (1,2-methanofullerene C60) - 61,61-dicarboxylic acid and esters thereof such as the diethyl ester; (1,2-methanofullerene C70)-71,71-dicarboxylic acid and esters thereof such as the diethyl ester; [6,6]-phenyl C61 butyric, [6,6]-phenyl C71 butyric and [6,6]-phenyl C85 butyric acids and esters thereof such as the methyl, ethyl, propyl, butyl, octyl, dodecyl and polyethylene glycol esters, bis-{6,6J-phenyl C61 butyric, bis-[6,6]-phenyl C71 butyric and bis-[6,6J-phenyl C85 butyric acids and esters thereof; and {6,6]-thienyl C61 butyric, [6,6]-thienyl C71 butyric and [6,6}-thienyl C85 butyric acids and esters thereof. Suitable esters of any of the above preferred fullerene carboxylates include alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl and alkynylaryl esters which may be optionally substituted.

Preferably any fullerene derivative comprises at least one carbon-carbon or carbon-nitrogen double bond, preferably as part of the closed-cage structure. Preferably any fullerene derivative is not functionalised with one or more further fullerenes or further fullerene derivatives.

As used herein, the term group' used in relation to a metal refers to a group of the periodic table numbered from left to right in accordance with the JUPAC Periodic Table of the Elements published 1 November 2004. Thus, a non-group I metal refers to any metallic element other than Li, Na, K, Rb, Cs or Fr.

In a first embodiment of the first aspect of the present invention, M is a group 2 or a transition metal, i.e. a metaijic element selected from Be, Mg, Ca, Sr, Ba or Ra or a d-block metallic element of groups 3 to 12 of the periodic table. Preferably M is a transition metal. Preferably M is selected from a transition metal of groups 8 to 10 of the periodic table, preferably selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt.

More preferably M is selected from Ni, Pd or Pt, most preferably M is Pd.

In a second embodiment of the first aspect of the present invention, the oxidation state of M is between (0) and (VII), preferably between (0) and (IV), more preferably is (0), (II) or (IV) and most preferably is (0).

In a preferred third embodiment, M is Pd(0).

In a fourth embodiment of the first aspect of the present invention, each M-L bond has an approximate bond dissociation enthalpy of less than that of an average M-C bond. Preferably each M-L bond has an approximate bond dissociation enthalpy of less than about 610 kJmol', less than about 436 kJmol1 or less than about 337 kJmoY1. Most preferably each M-L bond has an approximate bond dissociation enthalpy of less than about 436 kJmol1.

As used herein, the term approximate bond dissociation enthalpy' in relation to each M-L or M-L' bond refers to the enthalpy change for the dissociation M_A(g) > I\41(g) + A(g) wherein A refers to the atom of the ligand L or L' that is bonded to the metal in the M-L or M-L' bond in question. Similarly, as used herein the term approximate bond dissociation enthalpy' in relation to an average M-C bond' refers to the enthalpy change for the dissociation: MC(g) Mg + C(g) Values for such enthalpy changes can be found for instance by reference to standard tables well known to those skilled in the art, such as those listed in the CRC Handbook of Chemistry and Physics, 87tI Ed., 2006-2007, from page 9-54.

As used herein, the term ligand' refers to any ion or molecule capable of donating and/or sharing electrons. Preferably the ligands are anionic ligands or neutral donor ligands.

A ligand may be a monodentate ligand, i.e. a ligand bound to the central metal atom M via a single donor group.

Suitable neutral donor monodentate ligands include but are not limited to OR2, SR2, NR3, PR3, AsR3, SbR3, RCEN, RNC, N2, NO, CO and CS, wherein each R is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group. Optionally any two or more R groups together with the central ligand atom to which they are attached may together form a ring. Preferred neutral donor monodentate ligands include OR2, SR2, NR3 and PR3, more preferably NR3 and PR3, most preferably PR3. Preferably each R is independenfly selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, atyl, arylalkyl, or alkylaryl group. More preferably, each R is independently selected from an optionally substituted alkyl or aryl group. A particularly preferred neutral donor monodentate ligand is PPh3.

Suitable anionic monodentate ligands include but are not limited to R, R0, RS R2N, CN, SCN, and R2P, wherein each R is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group. Optionally any two or more R groups together with the central ligand atom to which they are attached may together form a ring. Preferred anionic monodentate ligands include F, C, Bi, F, R0 and RS. Preferably each R is independently selected from hydrogen or an optionally substituted alkyl, aryl, arylalkyl, or alkylaryl group. More preferably, each R is independently selected from an optionally A ligand may also be attached to a central metal atom M or M' via a double (e.g. M=L or M=L') or a triple (e.g. MEL or MEL') bond. Examples of such double or triple bonds include but are not limited to M=O, M=S, M=NR, M=CR2, MEN and MECR bonds and the equivalent M' double or triple bonds, wherein each R is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group. Optionally any two or more R groups together with the central ligand atom to which they are attached may form a ring.

Preferably the metal complex of any aspect of the present invention comprises no M=L or MEL bonds. Preferably the metal complex of any aspect of the present invention comprises no ML' or MEL' bonds. Preferably the metal complex of any aspect of the present invention comprises no ML", M'L", MEL" or M'EL" bonds.

A ligand may also be attached to a central metal atom M or M' side-on' via a it-complex. Examples of ligands that are able to form such it-complexes include but are not limited to R2CCR2, RCECR and R2CNR, wherein each R is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group. Optionally any two or more R groups together with the central ligand atom(s) to which they are attached may form a ring. Preferably such ligands have a delocalised it-system such as R2CCR-CR2, possess two or more conjugated double bonds such as R2CCR-RCCR2, or are aromatic such as a cyclopentadienyl ligand Such hgands may be i2-, -, -, ,-, ,-or f-bonded, wherein the superscript number denotes the number of contiguous atoms in the ligand coordinated to the central metal atom M or M'. Preferably none of the ligands L, L' or L" in any aspect of the present invention is a r-complex ligand, i.e. all of the ligands L, L' and L" have a hapticity of 1.

A ligand may also be a further metal complex, such as M'L"Z, wherein M' is a non-group 1 metal, each L" is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein z is an integer between 0 and 9. Each M'L"2 may be coordinated to the central metal atom M of MLWL'X either directly via a M-M' bond, or via a bridging group wherein at least one of the ligands L" is divalent to give a MLtIM! bond. Suitable divalent ligands include a -F-, -Cl-, -Br-, -I-, -0-, -5-or -NR-group, or an optionally substituted alkylene, alkenylene, alkynylene, arylene, arylalkylene, arylalkenylene, arylalkynylene, alkylarylene, alkenylarylene or alkynylarylene group, or any polydentate ligand as outlined below. M' may be any metallic element in any oxidation state that M may be according to any embodiment of the first aspect of the present invention. Each M and M may be the same or different. Preferably each M' is the same as M. Each L" may be any ligand that L or L' may be according to any embodiment of the first aspect of the present invention.

Preferably all L" that are not part of a M-L"-M' bond are the same. Optionally all L" that are not part of a M-L"-M' bond are the same as all remaining ligands L and/or L' attached to M. Preferably z is an integer between 1 and 8, more preferably z is an integer between 2 and 6, more preferably z is 4. In one embodiment of any aspect of the present invention, no more than four atoms M and M' are present within a single metal complex including any further metal complexes. Preferably no more than three atoms, even more preferably no more than two atoms M and M' are present within a single metal complex. In a preferred embodiment of any aspect of the present invention, no ligand is a further metal complex, such as M'L"Z.

As used herein, the term polydentate ligand' refers to a ligand bound to a central metal atom M or M' via two or more donor groups. Such a ligand may be bidentate (i.e. bound via two donor groups), tridentate (i.e. bound via three donor groups), tetradentate (i.e. bound via four donor groups) or multidentate (i.e. bound via five or more donor groups).

Suitable polydentate ligands include but are not limited to ligands formed from two or more substituents selected from OR2, SR2, NR3, PR3, AsR3, SbR3, RCEN, RNC, R, R0, RS R2N, R2P, =NR, =CR2, ECR, R2C=CR2, RCECR and R2C=NR, wherein each R group is independently selected from hydrogen, halogen such as F, Cl, Br or I, or an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group, and wherein at least one R group on each substituent forms together with an R group on another substituent a covalent bond, a -0-, -S-or -NR-group, or an optionally substituted alkylene, alkenylene, alkynylene, arylene, arylalkylene, arylalkenylene, arylalkynylene, alkylarylene, alkenylarylene or alkynylarylene group, such that the two or more substituents selected are linked together by covalent bonding. Preferably such polydentate ligands are formed from two or more substituents selected from OR2, SR2, NR3, PR3, R, R0, RS R2N and R2P. Examples of suitable polydentate ligands include bidentate ligands such as 2,2-bipyridene, (MeCOCHCOMe), H2NCH2CH2NH2 and H2NCH2CO2, tridentate ligands such as diethylenetriamine and terpyridine, tetradentate ligands such as triethylenetetramine and tetraazocyclotetradecane, and multidentate ligands such as EDTA, crown ethers and cryptands.

In a preferred embodiment of any aspect of the present invention, the ligands L, L' and/or L" are not fullerenes or fullerene derivatives.

For the purposes of the present invention, an "alkyl" group is defined as a monovalent saturated hydrocarbon, which may be straight-chained or branched, or be or include cyclic groups. An alkyl group may optionally include one or more heteroatoms N, 0 or S in its carbon skeleton. Examples of alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and n-pentyl groups. Preferably an alkyl group is straight-chained or branched and does not include any heteroatoms in its carbon skeleton. Preferably an alkyl group is a C1-C12 alkyl group, which is defined as an alkyl group containing from I to 12 carbon atoms. More preferably an alkyl group is a C1-C6 alkyl group, which is defined as an alkyl group containing from I to 6 carbon atoms. An "alkylene" group is similarly defined as a divalent alkyl group.

An "alkenyl" group is defined as a monovalent hydrocarbon, which comprises at least one carbon-carbon double bond, which may be straight-chained or branched, or be or include cyclic groups. An alkenyl group may optionally include one or more heteroatoms N, 0 or S in its carbon skeleton. Examples of alkenyl groups are vinyl, allyl, but-1-enyl and but-2-enyl groups. Preferably an alkenyl group is straight-chained or branched and does not include ay heteroatoms in its carbon skeleton. Preferably an alkenyl group is a C2-C12 alkenyl group, which is defined as an alkenyl group containing from 2 to 12 carbon atoms. More preferably an alkenyl group is a C2-C6 alkenyl group, which is defined as an alkenyl group containing from 2 to 6 carbon atoms. An "alkenylene" group is similarly defined as a divalent alkenyl group.

An "alkynyl" group is defined as a monovalent hydrocarbon, which comprises at least one carbon-carbon triple bond, which may be straight-chained or branched, or be or include cyclic groups. An alkynyl group may optionally include one or more heteroatoms N, 0 or S in its carbon skeleton. Examples of alkynyl groups are ethynyl, propargyl, but-1-ynyl and but-2-ynyl groups. Preferably an alkynyl group is straight-chained or branched and does not include any heteroatoms in its carbon skeleton. Preferably an alkynyl group is a C2-C12 alkynyl group, which is defined as an alkynyl group containing from 2 to 12 carbon atoms. More preferably an alkynyl group is a C2-C6 alkynyl group, which is defined as an alkynyl group containing from 2 to 6 carbon atoms. An "alkynylene" group is similarly defined as a divalent alkynyl group.

An "aryl" group is defined as a monovalent aromatic hydrocarbon. An aryl group may optionally include one or more heteroatoms N, 0 or S in its carbon skeleton.

Examples of aryl groups are phenyl, naphthyl, anthracenyl and phenanthrenyl groups. Preferably an aryl group does not include any heteroatoms in its carbon skeleton. Preferably an aryl group is a C4-C14 aryl group, which is defined as an aryl group containing from 4 to 14 carbon atoms. More preferably an aryl group is a C6-C10 aryl group, which is defined as an aryl group containing from 6 to 10 carbon atoms. An "arylene" group is similarly defined as a divalent aryl group.

For the purposes of the present invention, where a combination of groups is referred to as one moiety, for example, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl, the last mentioned group contains the atom by which the moiety is attached to the rest of the molecule. A typical example of an arylalkyl group is benzyl.

For the purposes of this invention, an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group or an optionally substituted alkylene, alkenylene, alkynylene, arylene, arylalkylene, arylalkenylene, arylalkynylene, alkylarylene, alkenylarylene or alkynylarylene group or an optionally substituted hydrocarbon may be substituted with one or more of -F, -Cl, -Br, -I, -CF3, -Cd3, -CBr3, -CT3, -OH, -SH, -NH2, -CN, -NO2, -COOH, RUORP, -R°-S-R, -R'-SO-R, -R-SO2-R, -R-SO2-OR, -RO-SO2-R, -R-SO2-N (R)2, -R-NR-SO2-R, RaOSO2OR, -R0-SO2-N(R)2, -R-NR-S02-OR, -R-NR-SO2-N (R)2, _R_N(R)2, -Ru-N (R)3, -R-P(R)2, -R-Si(R)3, -R-CO-R, -R-CO-OR, -RO-CO-R, -R-CO-N(R)2, -R-NR-CO-R, -RO-CO-OR, -RO-CO-N(R)2, -R-NR-CO-N(R)2, -R-CS-R, -R-CS-OR, -RO-CS-R, -R-CS-N(R)2, -R-NR-CS-R, -RO-CS-OR, -RO-CS-N (R)2, -R-NR-CS-OR, -R-NR-CS-N(R)2, -Rn, a bridging substituent such as -0-, -S-, -NR-or -Ru-, or a it-bonded substituent such as 0, S or NR.

In this context, is independently a chemical bond, a C1-C10 alkylene, C1-C10 alkenylene or C1-C10 alkynylene group. -R is independently hydrogen, unsubstituted C1-C6 alkyl or unsubstituted C6-C10 aryl. Optional substituent(s) are not taken into account when calculating the total number of carbon atoms in the parent group substituted with the optional substituent(s). Preferably an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group is not substituted with a bridging substituent.

Preferably an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group is not substituted with a it-bonded substituent. Preferably a substituted group comprises 1, 2 or 3 substituents, more preferably 1 or 2 substituents, and even more preferably 1 substituent.

Any optional substituent may be protected. Suitable protecting groups for protecting optional substituents are known in the art, for example from "Protective Groups in Organic Synthesis" by T.W. Greene and P.G.M. Wuts (Wiley-Interscience, 4th edition, 2006).

In a fifth embodiment of the first aspect of the present invention, each L is a monodentate ligand.

In a sixth embodiment of the first aspect of the present invention, each L is the same. Preferably each L is PPh3.

In a seventh embodiment of the first aspect of the present invention, each M-L' bond has an approximate bond dissociation enthalpy of less than that of an average M-C bond. Preferably each M-L' bond has an approximate bond dissociation enthalpy of less than about 610 kJmoY1, less than about 436 kJmol1 or less than about 337 kJmol'. Most preferably each M-L' bond has an approximate bond dissociation enthalpy of less than about 436 kJmol'.

In an alternative to the seventh embodiment, each M-L' bond has an approximate bond dissociation enthalpy greater than that of an average M-C bond Preferably each M-L' bond has an approximate bond dissociation enthalpy greater than about 610 kJmoY1, greater than about 436 kJmol1 or greater than about 337 kJmol1. Most preferably each M-L' bond has an approximate bond dissociation enthalpy greater than about 436 kJmol1.

In an eighth embodiment of the first aspect of the present invention, each L' is a monodentate ligand.

In a ninth embodiment of the first aspect of the present invention, each L' is the same. Preferably each L' is PPh3.

In a tenth embodiment of the first aspect of the present invention, all L and U are the same.

In an eleventh embodiment of the first aspect of the present invention, w is an integer between 0 and 6, or an integer between I and 4, or an integer between I and 3. Preferably w is 2.

In a twelfth embodiment of the first aspect of the present invention, x is an integer between 0 and 6, preferably x is an integer between 0 and 4. Preferably x is 2.

In a thirteenth embodiment of the first aspect of the present invention, 2 w + x 8, preferably 3 w + x 6. Preferably w + x = 4.

In a preferred fourteenth embodiment, the metal complex MLWL'X is Pd(PPh3)4.

The metal complex MLWL', of the first aspect of the present invention may be charged or uncharged. Preferably the overall charge on said complex is between -8 and +8, more preferably between -4 and +4 and more preferably still between -2 and +2. Most preferably the metal complex MLWL'X of the first aspect of the present invention is uncharged.

In any aspect of the present invention, where a metal complex such as MLWLX, ML, or ML'X complexed to one or mote fullerenes or fullerene derivatives, is charged, it is preferably accompanied by one or more suitable counter-ions. Where the metal complex is positively charged, suitable counter anions include but are not limited to halides (such as fluoride, chloride, bromide or iodide counter anions) or other inorganic counter anions (for example, nitrate, perchlorate, sulphate or phosphate counter anions); or organic counter anions such as organic carboxylates (for example, propionate, butyrate, glycolate, lactate, mandelate, citrate, acetate, benzoate, salicylate, succinate, malate or hydroxysuccinate, tartarate, fumarate, maleate, hydroxymaleate, mucate or galactarate, gluconate, pantothenate or pamoate anions), organic sulphonates (for example, methanesulphonate, trifluoromethanesuiphonate, ethanesuiphonate, 2-hydroxyethanesulphonate, benzenesulphonate, toluene-p-sulphonate, naphthalene-2-sulphonate or camphorsuiphonate anions) or anions of amino acids (for example, ornithinate, glutamate or aspartate anions). Preferred counter anions include halide, sulphate, phosphate or organic counter anions. A particularly preferred counter anion is chloride. Where the metal complex is negatively charged, suitable counter cations include but are not limited to lithium, sodium, potassium, magnesium, calcium and ammonium. A particularly preferred counter cation is sodium.

In a fifteenth embodiment of the first aspect of the present invention, the fullerene or fullerene derivative is selected from C60, C70, C76, C78, and C84. Preferably the fullerene is C60 or C70. Most preferably the fullerene is C60.

As used herein, the term substantially soluble' refers to a solute with a solubility in the specified solvent of at least 0.01 mg/mi at 25°C and 1 atmosphere pressure.

Preferably the solute has a solubility of at least 0.1 mg/mi, more preferably at least 0.5 mg/mI, more preferably at least 1 mg/mI and most preferably at least 2 mg/mi.

As used herein, the term substantially insoluble' refers to a solute with a solubility in the specified solvent of less than 0.01 mg/mi at 25°C and I atmosphere pressure.

Preferably the solute has a solubility of less than 0.001 mg/ml, more preferably less than 0.0001 mg/ml and most preferably less than 0.00001 mg/mi.

The solubility of a solute in a given solvent may readily be determined experimentally by the person skilled in the art or by reference to standard tables such as those given for instance for C60 in Marcus et al., J. Phys. Chem. B., 2001, vol. 105, pp. 2499-2506.

In a sixteenth embodiment of the first aspect of the present invention, the first solvent is an optionally substituted hydrocarbon which may include one or more heteroatoms N, 0, S or Si in its carbon skeleton, or is carbon disulphide. Preferably the first solvent is a non-polar solvent. Preferably the first solvent is liquid at 25°C and 1 atmosphere pressure.

Preferably the optionally substituted hydrocarbon is unsubstituted or is substituted with one or more of -F, -Cl, -Br or -I. Preferably, where the optionally substituted hydrocarbon includes one or more heteroatoms N, 0 or S in its carbon skeleton, said heteroatoms are included in an aromatic portion of said hydrocarbon.

Preferably the first solvent is selected from I -chloronaphthalene, I -methylnaphthalene, I,2-dichlorobenzene, chlorobenzene, 1,2,4-trimethylbenzene, xylene, tetrahydronaphthalene, pyridine, carbon disuiphide, 1,2,3-tribromopropane, bromoform, toluene, benzene or cyclohexane.

Preferably the first solvent is an aromatic hydrocarbon. Said aromatic hydrocarbon may optionally include one or more heteroatoms N, 0 or S in its carbon skeleton and may be unsubstituted or substituted. In one embodiment the aromatic hydrocarbon is substituted with one or more groups selected from -F, -Cl, -Br, -I or -R2, wherein each R2 contains I to 10 carbon atoms and is selected from an alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group any of which may be unsubstituted or substituted with one or more groups selected from -F, -Cl, -Br or -I. Preferably R2 does not include any heteroatoms in its carbon skeleton. Preferably each R2 contains 1 to 6 carbon atoms.

Preferably the aromatic hydrocarbon does not include any heteroatoms in its carbon skeleton.

Preferred aromatic hydrocarbons include 1-chloronaphthalene, 1 -methylnaphthalene, I,2-dichlorobenzene, chlorobenzene, 1,2,4-trimethylbenzene, xylene, tetrahydronaphthalene, pyridine, toluene and benzene. Most preferably the first solvent is toluene.

In a seventeenth embodiment the second solvent is a polar protic or a polar aprotic solvent. Preferably the second solvent is liquid at 25°C and 1 atmosphere pressure.

Preferred polar protic solvents include alcohols, carboxylic acids and amines.

Preferred polar aprotic solvents include N,N-dimethylformamide, dimethylsuiphoxide, acetonitrile, esters such as ethyl acetate and ketones such as acetone.

Preferably the second solvent is an alcohol. Preferably the alcohol is R3OH, wherein R3 is selected from an optionally substituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl or alkynylaryl group. Preferably R3 is an optionally substituted alkyl or arylalkyl group. Preferably the alcohol is monohydric.

Preferably R3 is an optionally substituted C8 alkyl group, more preferably R3 is an optionally substituted C26 alkyl group. Preferably the alcohol is methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, 2-methyl-i -propanol, t-butanol, I -pentanol, cyclopentanol, i-hexanol, cyclohexanol, 1-heptanol or 1-octanol. Most preferably the alcohol is isopropanol.

In an eighteenth embodiment of the first aspect of the present invention, the metal complex is substantially soluble in the first solvent. Alternatively or in addition, the metal complex may be substantially soluble in the second solvent.

In a nineteenth embodiment, the metal complex is substantially insoluble in the second solvent. Alternatively, the metal complex may be substantially insoluble in the first solvent.

In a twentieth embodiment of the first aspect of the present invention, the first and second solvents are substantially miscible.

As used herein, the term substantially miscible' in relation to two liquids A and B means that when mixed together at 25°C and 1 atmosphere pressure, A and B form a single phase between any two mole fractions of B, XB1 and x82, wherein the magnitude of x5 ( x2 -xBl) is at least 0.05. For example, A and B may form a single phase where the mole fraction of B, XB is from 0.40 to 0.45, or from 0.70 to 0.75; in both cases LXB = 0.05.

Preferably, the magnitude of 1x8 is at least 0.10, more preferably at least 0.25, more preferably at least 0.50, more preferably at least 0.75, more preferably at least 0.90, even more preferably at least 0.95. Most preferably the term substantially miscible' in relation to two liquids A and B means that when mixed together at 20°C and I atmosphere pressure, A and B form a single phase when mixed together in any proportion.

In a twenty-first embodiment, a surfactant is added to the first and/or second solvent. A surfactant may be used for instance to allow two otherwise immiscible solvents to become substantially miscible, to improve the miscibility of two solvents, or to improve the solubility of a component (e.g. a fullerene, fullerene derivative or a metal complex) in one or more of the solvents.

The surfactant used may be an ionic or non-ionic surfactant and may be selected from any conventional surfactant type including alkanolamides; alkoxylated derivatives of alcohols, alkyl phenols, amines, amides, fatty acids, fatty esters and oils; amine acetates and oxides; aryl, alkyl, arylalkyl and alkylaryl sulfonates and sulfates; betame derivatives; carboxylated alcohol ethoxylates; esters of fatty acids, glycols, glycerols, sucrose, glucose and phosporic acid; fluorocarbon-based surfactants; imidazolines, imadazolines and other heterocydic surfactants; isethionates; lanolin-based derivatives; lecithin and lecithin derivatives; lignin and lignin derivatives; polysaccharides, polyacrylates, polyacrylamides, and other polymeric and block polymeric surfactants; protein-based surfactants; quaternary ammonium surfactants; sarcosine derivatives; silicone-based surfactants; soaps; sorbitan derivatives; sulfates and sulfonates of amines, amides, olefins, petroleum, oils, fatty acids, fatty esters, ethoxylated alcohols and ethoxylated alkyl phenols; sulfosuccinates and sulfosuccinamates; taurates; and thio, mercapto and phosphorous derivatives.

Preferable surfactants include alkylaryl polyethylene glycols, alkyl polyethylene glycols, salts of dodecylated oxydibenzene disulfonate, ethoxylated nonyiphenol sutfactants, aliphatic polyoxyethylene ether surfactants, polyoxyethylene alkyl ether surfactants, and castor oil derivatives.

-19 -In a twenty-second embodiment of the first aspect of the present invention, the fullerene and/or fullerene derivative is combined with the first solvent prior to admixture with the metal complex and with the second solvent. Optionally in this embodiment the metal complex is combined with the first solvent prior to admixture with the second solvent. Alternatively the metal complex is combined with the second solvent prior to the admixture of the first and second solvent.

In a twenty-third embodiment of the first aspect of the present invention, the metal complex is combined with the first solvent prior to admixture with the fullerene and/or fullerene derivative and with the second solvent. Optionally in this embodiment the fullerene and/or fullerene derivative is combined with the first solvent prior to admixture with the second solvent.

Optionally in either of the twenty-second or twenty-third embodiments, the fullerene and/or fullerene derivative is combined with the first solvent to a concentration of from 1 x 10 to 0.1 molL1, more preferably of from I x iO to 0.01 molL1, more preferably of from 1 x i03 to 5 x iO molL1, most preferably of about 3.5 x 1O molL1. Optionally in either of the twenty-second or twenty-third embodiments, the fullerene and/or fullerene derivative is combined with the first solvent to form a saturated solution.

Optionally in either of the twenty-second or twenty-third embodiments, where the metal complex is combined with the first or the second solvent, it may be done to a concentration of from 1 x to 0.1 molL1, more preferably of from 1 x iO to 0.01 molL1, more preferably of from 1 x iO to 5 x 10 molL1, most preferably of about 3.5 x 10 moIJ1. Optionally in either of the twenty-second or twenty-third embodiments, the metal complex is combined with the first or the second solvent to form a saturated solution.

Optionally in either of the twenty-second or twenty-third embodiments, the first solvent is added to the second solvent. Preferably, the first solvent is added drop-wise, i.e. in the form of droplets. Preferably said droplets have an average diameter of less than about 1mm, more preferably of less than about 500pm, more preferably of less than about 100tm, most preferably of less than about 50}lm.

The first solvent may optionally be added to the second solvent at a rate of between 0.01 and 10 mi/mm per ml of the second solvent. More preferably a rate of between 0.1 and I mi/mm per ml of the second solvent is used, most preferably a rate of about 0.25 mi/mm per ml of the second solvent is used.

Optionally in either of the twenty-second or twenty-third embodiments, the second solvent is added to the first solvent. Preferably, the second solvent is added drop-wise, i.e. in the form of droplets. Preferably said droplets have an average diameter of less than about 1mm, more preferably of less than about 500p.m, more preferably of less than about 100tm, most preferably of less than about 50rm.

The second solvent may optionally be added to the first solvent at a rate of between 0.01 and 10 ml/min per ml of the first solvent. More preferably a rate of between 0.1 and I ml/min per ml of the first solvent is used, most preferably a rate of about 0.25 mi/mm per ml of the first solvent is used.

In a twenty-fourth embodiment of the first aspect of the present invention, the metal complex (a), the fullerene and/or fuilerene derivative (b), and the first solvent (c) are in contact for less than 30 minutes prior to admixture with the second solvent. Preferably the three components (a) to (c) are in contact for less than 10 minutes prior to admixture with the second solvent, more preferably the three components (a) to (c) are in contact for less than 5 minutes prior to admixture with the second solvent, even more preferably the three components (a) to (c) are in contact for less than 1 minute prior to admixture with the second solvent. Most preferably the three components (a) to (c) are in contact for less than 30 seconds prior to admixture with the second solvent.

In a twenty-fifth embodiment, all four components (a)-(d) are mixed substantially simultaneously.

In a twenty-sixth embodiment of the first aspect of the present invention, the process is a continuous process for the preparation of fullerites.

In a twenty-seventh embodiment of the first aspect of the present invention, a mole ratio of the metal complex (a) to the fullerene and/or fullerene derivative (b) of between 1:10,000 and 1:1 is used. Preferably a mole ratio of (a):(b) of between 1:1,000 and 1:2 is used, more preferably a mole ratio of (a):(b) of between 1:500 and 1:5 is used, even more preferably a mole ratio of(a):(b) of between 1:100 and 1:10 is used. Most preferably a mole ratio of the metal complex (a) to the fullerene and/or to fullerene derivative (b) of about 1:19 is used.

In a twenty-eighth embodiment, said process is performed under an inert atmosphere. Preferably the inert atmosphere is selected from nitrogen or a noble gas. Most preferably the inert atmosphere is nitrogen or argon.

In a twenty-ninth embodiment of the first aspect of the present invention, said process further comprises the step of removing the supernatant after fullerite precipitation. Said supernatant may be removed for instance by evaporation, optionally under vacuum, or by decantation or filtration, optionally after the step of separating the precipitate by centrifugation. Preferably said supernatant is removed by filtration.

In a thirtieth embodiment of the first aspect of the present invention, said process further comprises the step of heating the precipitated fullerite, and/or subjecting the precipitated fullerite to irradiation, so as to convert a crystalline fullerite into a polymeric fullerite. Optionally the precipitated fullerite is heated using a laser.

Preferably, where the precipitated fullerite is heated, it is heated to a temperature of at least 50°C, at least 100°C, at least 200°C, or at least 300°C. Preferably, where the precipitated fullerite is heated, it is heated to a temperature of less than 600°C, more preferably to a temperature of less than 500°C.

A second aspect of the present invention relates to a process for the preparation of particles of ML', wherein M is a non-group I metal, wherein each L' is a li.gand, -22 -each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein y is an integer between 0 and 9, wherein said process comprises a process according to the first aspect of the present invention.

In one embodiment of the second aspect of the present invention, said process is for the preparation of particles of the metal M, i.e. of particles of ML', wherein y = 0.

In another embodiment, said process further comprises the step of dissolving the fullerite after precipitation to isolate the particles of ML' or M. Suitable solvents for dissolving the fullerite after precipitation may include any solvent suitable as a first solvent according to the first aspect of the present invention.

A third aspect of the present invention relates to a fullerite preparable according to a process of the first aspect of the present invention A fourth aspect of the present invention relates to a fullerite comprising ML'X complexed to one or more fullerenes and/or fullerene derivatives, wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein x is an integer between 0 and 8, and wherein said fullerite does not comprise a faceted end.

As used herein, the term end' in relation to a fullerite refers to any surface or group of surfaces at an extremity of the fullerite that are not substantially parallel to the longitudinal axis of the fullerite. As used herein, a faceted' end refers to an end comprising more than one surface, as illustrated for example in Figure 10.

For the avoidance of doubt, it should be noted that the geometric nature of the end surface or surfaces of the fullerite is, for the purposes of the present invention, to be evaluated as if any particles, clusters or other imperfections attached to or associated with said surface(s) do not exist.

In one embodiment of the fourth aspect of the present invention, the end surface of said fullerite is substantially perpendicular relative to the longitudinal axis of the fullerite.

In another embodiment, the end surface of said fullerite is substantially planar.

A fifth aspect of the present invention relates to a fullerite comprising ML'X complexed to one or more fullerenes and/or fullerene derivatives, wherein said IC fullerite further comprises particles of MLt on the surface of said fullerite, wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein x is an integer between 0 and 8, and wherein y is an integer between 0 and 9.

In one embodiment of the fifth aspect of the present invention, said particles are approximately spherical.

In another embodiment, said particles have an average diameter of between 0.1 and 100 nm. Preferably said particles have an average diameter of between 0.2 and 50 nm, more preferably between 0.5 and 20 nm. Most preferably said particles have an average diameter of between I and 6 nm.

In one embodiment of the fifth aspect of the present invention, y is an integer between 0 and 8, preferably y is an integer between 0 and 6, more preferably y is an integer between 0 and 4. Most preferably y is 0.

In another embodiment, said fullerite does not comprise a faceted end. Preferably the end surface of said fullerite is substantially perpendicular relative to the longitudinal axis of the fullerite. Preferably the end surface of said fullerite is substantially planar.

In one embodiment of either the fourth or fifth aspect of the present invention, M is a group 2 or a transition metal, i.e. a metallic element selected from Be, Mg, Ca, Sr, Ba or Ra or a d-block metallic element of groups 3 to 12 of the periodic table.

Preferably M is a transition metal. Preferably M is selected from a transition metal of groups 8 to 10 of the periodic table, preferably selected from Fe, Ru, Os, Go, Rh, Ir, Ni, Pd or Pt. More preferably M is selected from Ni, Pd or Pt, most preferably M is Pd.

In one embodiment of either the fourth or fifth aspect of the present invention, the oxidation state of M in ML'X and/or ML' is between (0) and (VII). Preferably the oxidation state of M in ML'X and/or ML' is between (0) and (IV) and more preferably is (0), (II) or (IV). Most preferably the oxidation state of M in ML'X and/or ML' is (0).

In any embodiment of the fifth aspect of the present invention, the oxidation state of M in ML'X and ML' may be the same or different. Preferably the oxidation state of M in ML'X and ML is the same.

In the fourth or fifth aspect of the present invention the metal complex of ML'X to one or more fullerenes and/or fullerene deivatives may be charged or uncharged.

Preferably the overall charge on said complex is between -8 and +8, more preferably between -4 and +4 and more preferably still between -2 and +2. Most preferably the metal complex of ML'X to one or more fullerenes and/or fullerene deivatives is uncharged.

In a preferred embodiment of either the fourth or fifth aspect of the present invention, M is Pd(0).

In one embodiment of either the fourth or fifth aspect of the present invention, each L' is a monodentate ligand.

In one embodiment of either the fourth or fifth aspect of the present invention, each L' is the same. Preferably each L' is PPh3.

-25 -In one embodiment of either the fourth or fifth aspect of the present invention, x is an integer between 0 and 6, preferably x is an integer between 0 and 4. Most preferably x is 2.

In one embodiment of either the fourth or fifth aspect of the present invention, the one or more fullerenes and/or fullerene derivatives are selected from C60, C70, C76, C78, and C84. Preferably the one or more fullerenes are C60.

IC In one embodiment of either the fourth or fifth aspect of the present invention, ML'X is complexed to the one or more fullerenes and/or fullerene derivatives via a i2-bond. Preferably said 12-bond is positioned across a bond forming one edge of both a 5-and a 6-membered ring of said fullerene or fullerene derivative.

Alternatively said i2-bond may be positioned across a bond forming one edge of two adjacent 6-membered rings of said fullerene or fullerene derivative.

In another alternative embodiment, ML'X is complexed to the one or more fullerenes and/or fullerene derivatives via a single atom of each of the one or more fullerenes and/or fullerene derivatives, or via a f-, ,-or 15-bond.

In one embodiment of either the fourth or fifth aspect of the present invention, each ML'X is complexed to a single fuflerene or fullerene derivative.

In one embodiment of either the fourth or fifth aspect of the present invention, each fullerene or fullerene derivative that is complexed to ML'X is complexed to a single ML'X.

In one embodiment of either the fourth or fifth aspect of the present invention, the fullerite comprises C60020s02(py)2, C60{ 020s02(py)2}2, C60020s02(4-tert-butylpyridine)2, C70 {020s02(py)2}, (12-C60) 0s3(CO)11, C60 {Os3(CO)1}2.

(2-C60)Os3(CO)10(I'TCMe), (2-C60)Os3(CO)10(PPh3), (2_C60)Os3(CO)9(PPh3)2, Ru3 (CO) 9(i.i3-i2,12,12-C60), Ru3C60, Os3(CO)9(3-12,2,12-C60), Ru5C 1(PPh3)-(t3_ 12,12,12-C60), Ru6C (CO)12(Ph2PCH2PPh2)(3-12,12,12-C60), Ru3(CO) ,(3-2,2,12-C70), {Ru3(CO),}2(t3-12,2,12-C70), (i2-C60)Fe(CO), (12-C60)Ru(CO)4, 1,2-(3,5- cyclohexadieno)C60-Fe(CO)3, [(C60)-{Ru(CH3CN)2(15-C5Me5) } 33+], C60Ru2(1.t-Cl) (pt-H) (i5-C5Me5)2, C60Ru2(i-Cl)2(vj5-C5Me5)2, C60S2Fe2(CO)6, C70 {S2Fe2(CO)6} where n = 1-4, (14-C6H7C60H)Fe(CO)3, (4-C7H9C60H)Fe(CO)3, (15-C5H4CH2C60H)Fe(15-C5H5), (i4-C6H7C60H)Ru(CO)3, (i2-C60)Ir(CO)C1(PPh3)2, C60 {Ir(CO)C1(PMe3)2}2, C60 {Ir(CO)Cl(PEt3)2}2, C60{Ir(CO)Cl(PEt3)2}, (12-Coo)Ir(CO)-Cl(Ph2PCH2C6H4OCH2C6H5)2, (12-C70) Ir(CO)Cl(PPh3)2, (2-C84) Ir(CO)C1(PPh3)2, (2-C60O)Ir(CQ)Cl(PPh3)2, (i2-C600)Ir(CO)Cl(AsPh3)2, (12-C6002) Ir(CO) Cl(PPh3)2, (i2-C700)Ir(CO)C1(PPh3)2, (12-C60) Ir(CO) (PPh3)3, C60 {Ir2Cl2(4-C8H12)2}2, (2-C60)Ir(CO) (f-C9H7), (2-C60)RhH(CO) (PPh3)2, (12-C70)Rh(CO) H-(PPh3)2, (12-C60)IrH(CO) (PPh3)2, (i2-C60)Rh(acac) (3,5-dimethylpyridine)2, C60 {Pt(PEt3)2}6, C60{Pt(PEt3)2}5, [(i2-C60)Pt-(PPh3)2], {(12-C60)Pt(PPh3)2]2, [(12-C60)Pt(PPh3)2]3, (,2-C60)Pt {P(OPh)3} 2' (C70) {Pt(PPh3)2} where n = 1-4, (i2-C60)Pt(Ph2P(CH2)PPh2) where n = 2 or 3, (12-C60)Pd(PPh3)2 (12-C60)Ni(PPh3)2 or (12-C60)Pt(PPh3)2.

In a particularly preferred embodiment of either the fourth or fifth aspect of the present invention, the fullerite comprises (12-C60)Pd(PPh3)2. In alternate preferred embodiments of either the fourth or fifth aspect of the present invention, the fullerite comprises (12-C60) Ir(CO) C1(PPh3)2, (12-C60)Ni(PPh3)2 or (12-C60)Pt(PPh3)2.

In one embodiment of either the fourth or fifth aspect of the present invention, 50 to 99.99% by weight of the fullerite consists of fullerenes and/or fullerene derivatives not directly complexed to ML'X. Preferably 75 to 99.9%, more preferably 90 to 99% by weight of the fullerite consists of fullerenes and/or fullerene derivatives not directly complexed to ML'X. Most preferably about 95% by weight of the fullerite consists of fullerenes and/or fullerene derivatives not directly complexed to ML'X.

As used herein, the term directly complexed' in relation to a fullerene or a fullerene derivative refers to those fullerenes or fullerene derivatives which are ligated to the metal M of ML'X, but the term excludes further fullerenes or further fullerene -27 -derivatives that functionalise the fullerene or fullerene derivative which is itself ligated to the metal M of ML'.

In one embodiment of either the fourth or fifth aspect of the present invention, the crystal structure of the fullerite is substantially close packed. Preferably the crystal structure of the fullerite is substantially face-centred cubic. Alternatively the crystal structure of the fullerite may be substantially hexagonal close packed. Alternatively still the crystal structure of the fullerite may be a non-closed packed structure such as substantially body-centred cubic or primitive cubic.

In one embodiment of either the fourth or fifth aspect of the present invention, the fullerite further comprises clusters on the surface of said fullerite, said clusters comprising one or more fullerenes and/or fullerene derivatives. Preferably said clusters have an average diameter of between 10 and 250 nm, more preferably between 20 and 150 nm, most preferably between 50 and 100 nm.

In one embodiment of either the fourth or fifth aspect of the present invention, said fullerite has a length of between 0.5 and 10 Inn. Preferably said fullerite has a length of between I and 5 tm, more preferably said fullerite has a length of about 2.5 p.m In one embodiment of either the fourth or fifth aspect of the present invention, said fullerite has an average diameter of between 0.1 and 5 pm. Preferably said fullerite has an average diameter of between 0.5 and 2 pm, more preferably said fullerite has an average diameter of about 1 pm.

As used herein, the term average diameter' in relation to a fullerite refers to the mean width of said fullerite perpendicular to the longitudinal axis of said fullerite.

In one embodiment of any of the third, fourth or fifth aspects of the present invention, the fullerite has an electron mobility of at least 0.001 cm2V1s1.

Preferably the fullerite has an electron mobility of at least 0.01 cm2V1s1, more preferably of at least 0.1 cm2V1s1.

A sixth aspect of the present invention relates to a process for the preparation of particles of ML' wherein M is a non-group I metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein y is an integer between 0 and 9, said process comprising the step of dissolving a fullerite according to the third or fifth aspect of the present invention in a solvent to isolate the particles of ML'.

Suitable solvents for dissolving the fullerite after precipitation may include any solvent suitable as a first solvent according to the first aspect of the present invention.

In one embodiment of the sixth aspect of the present invention, said process is for the preparation of particles of the metal M, i.e. of particles of ML', wherein y = 0.

A seventh aspect of the present invention relates to a particle of ML' preparable according to a process of the second or sixth aspects of the present invention.

An eighth aspect of the present invention relates to a particle of the metal M preparable according to a process of the second or sixth aspects of the present invention.

A ninth aspect of the present invention relates to a particle of ML', wherein M is a non-group I metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein y is an integer between 0 and 9, and wherein said particle has an average diameter of between 0.1 and 100 rim.

In one embodiment of the ninth aspect of the present invention, said particle has an average diameter of between 0.2 and 50 nm, more preferably between 0.5 and 20 rim. Preferably said particle has an average diameter of between 1 and 6 rim.

In another embodiment of the ninth aspect of the present invention, said particles are approximately spherical.

In one embodiment of the ninth aspect of the present invention, ML' is the metal M,i.e.y=0.

In one embodiment of any of the second, sixth, seventh, eighth or ninth aspects of the present invention, M in the particles of ML' or the particles of M is a group 2 or a transition metal, i.e. a metallic element selected from Be, Mg, Ca, Sr, Ba or Ra or a d-block metallic element of groups 3 to 12 of the periodic table. Preferably M is a transition metal. Preferably M is selected from a transition metal of groups 8 to of the periodic table, preferably selected from Fe, Ru, Os, Go, Rh, Ir, Ni, Pd or Pt. More preferably M is selected from Ni, Pd or Pt, most preferably M is Pd.

In one embodiment of any of the second, sixth, seventh, eighth or ninth aspects of the present invention, the oxidation state of M in the particles of ML' or the particles of M is between (0) and (VII), preferably between (0) and (IV), more preferably is (0), (II) or (IV) and most preferably is (0).

Preferably, in any of the second, sixth, seventh, eighth or ninth aspects of the present invention, ML' or M is Pd(0).

In one embodiment of any of the second or fourth to ninth aspects of the present invention, ML' may be charged or uncharged. Preferably the overall charge on ML' is between -8 and +8, more preferably between -4 and +4 and more preferably still between -2 and +2. Most preferably ML' is uncharged.

In one embodiment of any of the second, or fourth to seventh, or ninth aspects of the present invention, each M-L' bond has an approximate bond dissociation enthalpy of less than that of an average M-G bond. Preferably each M-L' bond has an approximate bond dissociation enthalpy of less than about 610 kJmol1, less than about 436 kJmol1 or less than about 337 kJmol1. Most preferably each M-L' bond has an approximate bond dissociation enthalpy of less than about 436 kJmol1 -30 -In an alternative embodiment of any of the second, or fourth to seventh, or ninth aspects of the present invention, each M-L bond has an approximate bond dissociation enthalpy greater than that of an average M-C bond. Preferably each M-L' bond has an approximate bond dissociation enthalpy greater than about 610 kJmol1, greater than about 436 kJmol1 or greater than about 337 kJmol1. Most preferably each M-L' bond has an approximate bond dissociation enthalpy greater than about 436 kJmol1.

In one embodiment of any of the second, sixth, seventh or ninth aspects of the present invention, each L' is a monodentate ligand. In one embodiment, each L' is the same. Preferably each Lt is PPh3.

In one embodiment of any of the second, sixth, seventh or ninth aspects of the present invention, y is an integer between 0 and 8, preferably y is an integer between 0 and 6, more preferably y is an integer between 0 and 4. Most preferably y is 0.

A tenth aspect of the present invention relates to a process for embedding particles according to any of the seventh, eighth or ninth aspects of the present invention in a matrix, said process comprising forming the matrix around a fullerite according to the third or fifth aspect of the present invention.

As used herein, where a particle is embedded' in a surface, a part of said particle lies below the level of the surface and a part of said particle is exposed above or on the surface. Preferably at least 5%, at least 10%, at least 25%, at least 5O%, at least 75% or at least 90% of the particle lies below the level of the surface.

Said matrix may comprise any material that is capable of forming a solid around said fullerite without substantial damage to the fullerite. Preferably said matrix is formed using a liquid that is able to set, e.g. by polymerisation, or cool to a solid, e.g. at 25°C, around said fullerite.

In one embodiment of the tenth aspect of the present invention, said matrix comprises a polymer or a metal with the proviso that if the particles are metal and the matrix comprises metal, then the metal of the matrix is different to the metal of the particles. Preferably where the matrix comprises metal, the metal of the matrix has a melting point lower than the melting point or the decomposition temperature of the particles. Preferably where the matrix comprises a polymer, said polymer does not comprise a fullerene or a fullerene derivative.

In another embodiment of the tenth aspect of the present invention, said process further comprises a second step of dissolving the fullerite in a solvent to leave said particles embedded in an internal or external surface of said matrix. Preferably said process further comprises a third step of etching the internal and/or external surface of said matrix to leave said particles affixed to but proud of the surface of said matrix. The etching process may comprise for instance the use of a chemical such as an acid or a base, or the use of enzymatic degradation to remove a fine layer of the matrix material from the surfaces of the matrix. By removing only a fine layer of the matrix using an etching substance that degrades the particles at a lesser rate, or that does not degrade the particles at all, the particles will remain attached to the matrix but with a greater surface area exposed, thus enhancing for instance their catalytic activity.

Alternatively an etching substance that degrades the particles at a greater rate than it degrades the matrix may be used to remove the particles from the matrix leaving small particle-sized cavities in the matrix surface.

An eleventh aspect of the present invention relates to a matrix with particles affixed thereto, preparable by a process according to the tenth aspect of the present invention.

A twelfth aspect of the present invention relates to a matrix comprising particles according to any of the seventh, eighth or ninth aspects of the present invention affixed thereto, wherein the matrix comprises a polymer or a metal with the proviso -32 -that if the particles are metal and the matrix comprises metal, then the metal of the matrix is different to the metal of the particles.

In one embodiment of the twelfth aspect of the present invention, the particles are embedded in an internal or external surface of said matrix. Preferably where the matrix comprises metal, the metal of the matrix has a melting point lower than the melting point or the decomposition temperature of the particles. Preferably where the matrix comprises a polymer, said polymer does not comprise a fullerene or a fullerene derivative.

A thirteenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, as a catalyst.

In one embodiment of the thirteenth aspect of the present invention, said catalyst is a catalyst for reduction. Preferably, said catalyst is a catalyst for hydrogenation.

In one embodiment of the thirteenth aspect of the present invention, said catalyst is a catalyst for oxidation.

In one embodiment of the thirteenth aspect of the present invention, said catalyst is a catalyst for carbon-carbon bond formation.

In one embodiment of the thirteenth aspect of the present invention, said catalyst is used in heterogeneous catalysis.

A fourteenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, in the formation of carbon nanostructures.

Techniques suitable for the formation of carbon nanostructures such as chemical vapour deposition are well known to those skilled in the art and are outlined for instance in Terranova et al., Chem. Vap. Deposition, 2006, vol. 12, pp. 3 15-325.

A fifteenth aspect of the present invention relates to a process for the synthesis of carbon nanostructures, said process comprising heating a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, in the presence of a carbon-containing gas such as methane, acetylene or carbon monoxide. Optionally said process occurs in the presence of an electric field.

The carbon nanostructures of the fourteenth or fifteenth aspect of the present invention may be for instance carbon nanotubes, nanofibres or nanoshells.

Preferably the carbon nanostructures are carbon nanotubes. Most preferably the carbon nanostructures are single-walled carbon nanotubes.

A sixteenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, in an electronic application. Preferably said electronic application is an electrode, a semi-conductor, a transistor, an optical device, a solar cell, a light source such as a light emitting diode, a photodetector, or a data storage device.

A seventeenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, as an adsorbent or a membrane.

An eighteenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, in a fuel cell.

A nineteenth aspect of the present invention relates to the use of a fullerite according to the third, fourth or fifth aspects of the present invention, a particle according to the seventh, eighth or ninth aspects of the present invention, or a matrix according to the eleventh or twelfth aspects of the present invention, in a magnetic or electromagnetic application. Preferably said magnetic or electromagnetic application is a data storage device.

For the avoidance of doubt, insofar as is practicable any embodiment of a given aspect of the present invention may occur in combination with any other embodiment of the same aspect of the present invention. In addition, insofar as is practicable it is to be understood that any preferred or optional embodiment of any aspect of the present invention should also be considered as a preferred or optional embodiment of any other aspect of the present invention.

Description of the Figures

Figure 1: SEM images of fullerite rods grown (a) with a 1:19 TTPP:C60 (mol) ratio and (b) without TTPP. The scale bars in (a) and (b) are 5 p.m.

Figure 2: Average fullerite diameter (.) and length (A) as a function of moles of palladium added.

Figure 3: Raman spectra of C60, fullerites, Pd-fullerites and (12-C60)Pd(PPh3)2.

Figure 4: Room temperature photoluminescence spectra of C60, fullerites, and Pd-fullerites.

* -35-Figure 5: TGA of fullerites grown with a 1:19 TTPP:C60 (mol) ratio (solid line) and without TTPP (dotted line) Figure 6: Dark.(a) and bright (b) field 200 K STEM z-contrast image of fullerite grown with 1:19 TTPP:C60 (mol) ratio with 300 nm scale bars and high angle annular dark (c) and bright field (d) images of palladium clusters with 50 nm scale bars.

Figure 7: EDX collected with a small beam positioned on a cluster showing the presence of Pd. The Cu signal originates from the TEM grid.

Figure 8: 31P NMR of palladium decorated fullerites showing the presence of phosphorus Figure 9: 1H NMR of the product of 1-ethynyl-1-cyclohexanol to 1-vinyl-I-cyclohexanol conversion under Pd-fullerite catalyst after 7 hours sealed under a H2 atmosphere.

Figure 10: Illustration of a fullerite with a faceted end.

Examples

Materials C60 (99.5%) was purchased from Materials & Electrochemical Research Corporation.

Tetrakis(triphenylphosphine)palladium(0) (TTPP) (99%), toluene (HPLC grade) and isopropanol (HPLC grade) were purchased from Sigma-Aldrich. All materials were used as received.

Preparation of the Free Palladium Complex (ri2-C)Pd(PPh1J2 C60 reacts with tetrakis(triphenylphosphine)palladium (TTPP) in solution to give high yield of (12-C60)Pd(PPh3)2, in which fullerene is ligated in a 12 fashion as shown below: P)3PS PPh3 r � The product exhibited a distinct chlorophyll green colour and 31P NMR chemical shift of 24.9 ppm as previously reported. A reduction in symmetry of C60 was clearly shown by Raman spectroscopy (vide infra) in agreement with previous reports. In particular splitting of the --774 cm1 Raman peak and strong enhancement of the --710 cm1 Raman peak is observed. These characteristics coincide with those previously described elsewhere. This synthesis of 12-C60)Pd(PPh3)2 was undertaken prior to the formation of Pd-functionalised fuilerites to allow comparison of the materials.

Preparation of Palladium-Functionalised Fulle rites Solutions of various sized aliquots of TTPP (3.6 x i03 molL1) were added (drop-wise at a rate of 0.5 mLmin1 controlled by a syringe pump) into 2.. 0 ml (3.6 x i03 molL1) C60/toluene, to give samples with mole ratios of TTPP:C60 of 1:1, 1:2, 1:19, 1:32, 1:49, 1:99 and 1:199. Following this a further 2.0 ml of isopropanol was added to each sample (drop-wise at a rate of 0.5 mLmin1 controlled by a syringe pump) to initiate crystal growth. This entire process was performed under N2 atmosphere. The liquid turned brown upon addition of the isopropanol to the C60/toluene solution forming a suspension which was allowed to settle. The solid product was separated by filtration (50 nm PTFE filter paper).

Characterisation The nanostructures were characterized by scanning electron microscopy (SEM) (FEI, Quanta 200F) and scanning transmission electron microscopy (STEM) (Hitachi STEM HD2300A, operated at 200KeV, Schottky field-emission gun). For STEM investigations, the suspension was sonicated for 10 mm before being transferred to a holey carbon coated copper grid.

FTIR (Nicolet Protégé 460, KBr disk), Raman (Renishaw 2000 system, 782 nm excitation), and absorption (UV-Vis-NIR, Varian Cary 5000) spectroscopy was used to characterise C60, fullerites, Pd-fullerites and (12-C60)Pd(PPh3)2 under a N2 atmosphere. Photoluminescence (PL) (514 nm excitation, 60 mW) spectroscopy was undertaken of C60, fullerites and Pd-fullerites in ambient (air) conditions. PL spectra of free (12-C60)Pd(PPh3)2 were not obtained as rapid oxidation occurred.

Thermal gravimetric analysis (TGA) (Tg 760 series, Rheometric scientific) at a heating rate of 5°C/mm in condensed dry air using an aluminium pan was undertaken. Solid state 31P NMR were obtained using a Varian VNMRS spectrometer operating at 161.88 MHz (399.88 MHz for 1H). A 4mm (rotor o.d.) MAS probe was used. Solution 1H and 31P NMR experiments were undertaken using a Bruker DRX 500 spectrometer.

Figures 1(a) and 1(b) show SEM images of fullerite rods grown with and without TTPP. It is clearly observed that the addition of TTPP results in a distinct change in morphology. The typical aspect ratio of the rods grown without TTPP is 1:14 (length 5.6 i.m and diameter 0.4 p.m). For fullerites grown with 1:19 TTPP:C60 (mol) a typical aspect ratio of 1:3 (length 2.3 m and diameter 0.8 p.m) is obtained.

As the quantity of TTPP introduced is increased further a corresponding increase in fullerite diameter, accompanied by a decrease in fullerite length, results as summarised in Figure 2. When equal amounts of TTPP and C60 are used it is found that spherical precipitates are obtained approximately 1 im in diameter.

Accordingly, it can be seen that the addition of TTPP has a direct effect on the morphology of the fullerites with the amount added being inversely related to the fullerite length obtained. A smaller dependence on fullerite diameter was observed which increased with TTPP concentration.

-38 -Additives are often used during crystallization to control morphology and careful analysis is required to prove that palladium is attached to the fullerites rather than simply influencing growth, especially in light of the very low concentrations used.

Figure 3 shows the Raman spectra of C60, standard' fullerites, Pd-fullerites and free' (12-C60)Pd(PPh3)2. Comparison of the Ag (2) pentagonal pinch mode at --1468 cm1 reveals a modification of the molecular bonding in the Pd-fullerites compared to that of C60 and the standard fullerites. The broadening of this peak 1460 cm1 is very similar to that observed in the Raman spectrum of (12-C60)Pd(PPh3)2 which to shows a shoulder located -1458 cm1. Inspection of the C60 and (2-C60)Pd(PPh3)2 Raman peak --773 cmt clearly shows splitting of this peak in the later caused by the reduction in symmetry of C60. In addition the peak -708 cm1 is increased in prominence upon complexation. Similar effects can be observed by comparing the fullerite and Pd-fullerite spectra in this region. In the case of the Pd-fullerites the relative intensity of the --708 cm1 peak in increased with respect to the 773 cm1 peak. Furthermore, a number of additional peaks, close to the baseline, are observed in the Pd-fullerites at --722 and 732 cmt for example. The observed changes in the Pd-fullerite spectrum compared to the standard fullerites and the similarities with the changes in Raman spectra between (12-C60)Pd(PPh3)2 and C60 indicate that Pd is indeed attached to the fullerites grown in the presence of TTPP. The fact that the changes in spectra are small between the Pd-fullerites and standard fullerites is due to the small ratio of Pd-complexed C60 to uncomplexed C60 that is expected in the Pd-fullerites.

FTIR spectra of the same samples were obtained. In the case of (12-C60)Pd(PPh3)2 a series of peaks are observed (--521, 692 and 741 cm1) corresponding to the PPh3 groups. Corresponding peaks at --692 and 741 cm' are observed in the Pd-fullerites with the 521 cm1 peak obscured by the 527 cm1 peak of C60. Peaks characteristic of C60 are observed in all samples ("--527, 576, 1182, and 1429 cm1) except for (12-C60)Pd(PPh3)2in which the 576 cmt peak appears as a small shoulder and the 527 cm peak is obscured by the 521 cm1 PPh3 peak. In the Pd-fullerite and (f-C60)Pd(PPh3)2 spectra additional peaks are present at --802, 1016, 1101, and 1260 cm1 which may be due to residual solvent in the samples. These results confirm the -39 -presence of PPh3 within the Pd-fullerite samples but unlike the Raman do not provide direct evidence of Pd attachment to the C60.

The PL spectra of C60, fullerites and Pd-fullerites are shown in Figure 4. As stated above it was not possible to obtain the PL spectrum of (2-C60)Pd(PPh3)2 due to rapid oxidation of the complex. However, we note that the background in the Raman spectrum appears to peak at 16OO cm which corresponds to fluorescence peaking at 895 nm for the 782 nm excitation wavelength used. As previously reported the emission from C60 fullerites is significantly enhanced indicating increased Herzberg-Teller coupling between the F16 and 1Agvibronic states. In the case of Pd-fullerites there is a significant red-shift in the position of the main PL peak to -817 nm correlating with the shoulder observed in the PL spectra of C60 and the standard fullerites. There is also a shoulder at -91O nm clearly visible in the Pd-fullerites that is only weakly seen in the standard fullerites and C60 PL spectrum.

This shoulder coincides with the peak of the background signal recorded in the Raman spectra of the (12-C60)Pd(PPh3)2 complex at --895 nm (Figure 3). The shoulder at --760 nm in the Pd-fullerite PL corresponds with a similar very weak feature in the fullerite PL spectrum. It is also noticeable (through comparison of the noise level in the data) that the intensity of the Pd-Fullerite PL is reduced from that observed in the standard fullerites to a similar level as C60. These results, clearly showing that the emission is strongly affected, imply that the molecular electronic and vibronic states are significantly modified in the Pd-fullerites. This again supports the conclusion obtained from the Raman studies that Pd is attached to the C60 in these materials.

Figure 5 shows the TGA data of the two types of fullerites shown in Figures Ia and lb. Residues of 4.4 % and 1.2 % for fullerites formed with and without the presence of palladium, respectively, are observed indicating the presence of additional material. Additionally, the rate of combustion is observed to be higher for the fullerites grown in the presence of TTPP in the two temperatures regimes above and below --400°C. It is expected that any uncomplexed phosphine will be slowly oxidized to phosphine oxide and by 300°C is expected to have left the pan. The weight difference at 300°C between the fullerites grown with and without TTPP is approximately 3 %, which is very close to that expected based on the weight of the two uncomplexed PPh3 groups, supporting this hypothesis. At 600°C the higher residue observed for the palladium-fullerites at 600°C (again -3 %) is expected to result from PdO (m.p. 750°C) formed during heating. These results therefore provide additional qualitative evidence for the presence of palladium within the fullerites in addition to the observed affect of TTPP on fulierite growth, Raman, FTIR and PL studies.

To obtain further direct evidence that Pd is present in the fullerites STEM analysis was undertaken. Figures 6(a) and 6(b) show dark and bright field images of a fullerite grown using a 1:19 TTPP:C60 (mol) ratio. Figure 6(a) shows the presence of well defined highly dispersed point-like features along with much larger (> 50 nm) irregular shaped clusters. Such large clusters have not previously been observed in fullerites formed (without TTPP) using the FLLIP process. The large clusters can be seen to very clearly sit on the surface of the fullerites, Figure 6(b), and appear to be composed of C60 that may have been deposited following the fullerite growth. The appearance that the clusters are not in contact is an artefact of the limited contrast and brightness ranges available where the fullerite is at its thickest compared to its thinnest. Figure 6(c) and 6(d) show dark and bright field high magnification images of a large cluster in addition to a number of the smaller point-like features. These small features vary in size from -1.4 to 5.6 nm with a roughly spherical appearance.

Energy dispersive x-ray (EDX) analysis was undertaken to ascertain the composition of the smaller (< 5 nm) features and is shown in Figure 7. These features were found to contain palladium whereas other areas did not provide such a signal. This evidence in conjunction with the larger clusters demonstrates that some (12-C60)Pd(PPh3)2 complexes appears to have decomposed to elemental palladium which then aggregates to give the smaller (< 5 nm) particles shown in Figure 6.

To study further if (2-C60)Pd(PPh3)2 was present on the fullerites, in addition to elemental Pd particles, solid state 31P NMR was undertaken, Figure 8. Due to the low signal intensity obtained from solid state 31P NMR a cross polarization pulse sequence was used to give as high a signal-to-noise ratio as possible, collected over a period of 8 hours. For palladium-decorated fullerites, a number of peaks between and 40 ppm were observed. The most intense were at 23.4 and 26.6 ppm, close to the ligated (2-C60)Pd(PPh3)2 chemical shift at 25.4 ppm. Other possibilities for the large number of peaks include the oxidation of phosphine ligand to triphenylphosphine oxide which would be expected to be present in the region of 26.9 ppm (orthorhombic) and 28.6 ppm (monodinic). These results demonstrate that phosphorous is present within the sample and is therefore further supporting evidence of (12-C60)Pd(PPh3)2 being present.

In summary therefore, a fast, low-cost method for the preparation of Pd-fullerite catalysts through the introduction of TTPP into the FLLIP growth process of C0 fullerites has been demonstrated. FTIR and TGA analysis provides qualitative evidence for the presence of (12-C60)Pd(PPh3)2 within the fullerites formed during their growth. Raman, PL and solid state 31P NMR confirmed the presence of Pd and phosphorous thus further supporting the presence of (12-C0)Pd(PPh3)2 within the fullerites. Small Pd particles 1.4 -5.6 nm diameter (confirmed by EDX) are observed on the surface of the fullerites under STEM analysis.

Heterogeneous Catalysis To demonstrate catalytic behaviour of the palladium functionalized fullerites the hydrogenation of 1-ethynyl-1-cyclohexanol to 1-vinyl-1-cyclohexanol, as shown below, was studied. C Pd

A 100 ml glass reactor containing 6 mg Pd-fullerite catalyst (synthesized using 1:19 TTPP:C60) was first flushed with H2 for 10 minutes. The sealed reactor was left for minutes prior to 2.49 g of 1-ethynyl-1-cyclohexanol, dissolved in 30 ml of isopropanol, being added via a septum. The mixture was stirred at 60 rpm at room temperature throughout the reaction. Analytical samples of 0.2 ml were taken at hourly intervals (via a septum to minimize hydrogen loss). After each sample was taken, the reactor was flushed to replenish hydrogen gas for 10 minutes. The 0.2 ml solution containing the product was analysed by 1H NMR spectroscopy.

The starting reactant 1-ethynyl-1--cyclohexanol lacks any peaks in the chemical shift region between 4.5 to 7 ppm assigned to the alkene group, thus confirming that no alkene groups were present in the starting material, but present only following reaction. Over the course of the reaction hydrogenation occurs resulting in the appearance of alkene peaks, increasing in intensity up to an alkyne:alkene ratio of 9:1 after 7 hours, Figure 9. This corresponds to a conversion of approximately 10 % over the course of the experiment based on the relative change in NMR signal strength. Assuming H2 is an ideal gas with a 1:1 reaction of CC to H2 the maximum alkyne to alkene conversion for the quantity of H2 and 1-ethynyl-1-cyclohexanol used is expected to be 15 %. As a result the catalysis is 66 % efficient over this time period.

The demonstration of a heterogeneous system with catalytic activity corresponding to 66 % conversion of alkyne to alkene after 7 hours using a catalyst readily prepared by this method in a mater of minutes is a significant step in the reduction of time and therefore cost associated with the catalyst preparation. Previous catalytic work reported the optimum quantity of (12-C60)Pd(PPh3)2 to be 3 mg above which no increase the rate of hydrogenation occurs. The palladium equimolar amount corresponding to 3 mg of (i2-C60)Pd(PPh3)2 equates to 2.56 mg of TTPP precursor. In this study we carried out the catalysis using 6 mg of Pd-functionalized fullerites synthesized with a 1:19 TTPP:C60 ratio which corresponds to 0.47 mg of TTPP precursor as starting material. This represents an approximate order of magnitude reduction in the quantity of Pd precursor required to undertake similar catalysis. Previous work indicates that the reaction undertaken is due to the formation of the P-Pd-C bond in the (12-C60)Pd(PPh3)2 complex driven by the transfer of electron density from the P to Pd followed by further transfer to the C=C bond in the reactant. Given the reduction in P-Pd bonds within our catalyst due to the reduced amount of TTPP precursor used, and the additional fact that the presence of small Pd particles on the fullerite surface indicates a further reduction on P-Pd bonds, this indicates that the small Pd particles also play an important role in the catalytic process demonstrated.

It will be understood that the present invention has been described above by way of example only. The examples are not intended to limit the scope of the present invention. Various modifications and embodiments can be made without departing from the scope and spirit of the invention, which is defined by the following claims only.

Claims

Claims 1.A process for the preparation of a fullerite, said process comprising the admixture of (a) a metal complex MLWL'X, wherein M is a non-group I metal, wherein each L and Lt is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein w is an integer between 0 and 8 and x is an integer between 0 and 8, with the proviso that 2 w + x 9; (b) a fullerene and/or a fullerene derivative; (c) a first solvent in which the fullerene and/or fullerene derivative is substantially soluble; and (d) a second solvent in which the fullerene and/or fullerene derivative is substantially insoluble to precipitate the fullerite.
2. A process as claimed in claim I, wherein M is a group 2 or a transition metal.
3. A process as claimed in claim 2, wherein M is selected from a transition metal of groups 8 to 10.
4. A process as claimed in claim 3, wherein M is selected from Ni, Pd or Pt.
5. A process as claimed in claim 4, wherein M is Pd.
6. A process as claimed in any of claims 1 to 5, wherein the oxidation state of M is between (0) and (VII).
7. A process as claimed in claim 6, wherein the oxidation state of M is between (0) and (IV).
8. A process as claimed in claim 7, wherein the oxidation state of M is (0).
9. A process as claimed in any of claims I to 8, wherein M is Pd(0).
10. A process as claimed in any of claims I to 9, wherein each M-L bond has an approximate bond dissociation enthalpy of less than that of an average M-C bond.
11. A process as claimed in claim 10, wherein M is Pd, and each Pd-L bond has an approximate bond dissociation enthalpy of less than about 436 kJmoY'.
12. A process as claimed in any of claims 1 to ii, wherein each L is a monodentate ligand.
13. A process as claimed in any of claims I to 12, wherein each L is the same.
14. A process as claimed in any of claims I to 13, wherein each L is PPh3.
15. A process as claimed in any of claims I to 14, wherein each M-L' bond has an approximate bond dissociation enthalpy of less than that of an average M-C bond.
16. A process as claimed in claim 15, wherein M is Pd, and each Pd-L' bond has an approximate bond dissociation enthalpy of less than about 436 kJmol1.
17. A process as claimed in any of claims I to 16, wherein each L is a monodentate ligand.
18. A process as claimed in any of claims 1 to 17, wherein each L' is the same.
19. A process as claimed in any of claims 1 to 18, wherein all L and L' are the same.
20. A process as claimed in any of claims 1 to 19, wherein each L' is PPh3.
21. A process as claimed in any of claims I to 20, wherein w is an integer between 1 and 4.
22. A process as claimed in claim 21, wherein w is 2.
23. A process as claimed in any of claims I to 22, wherein x is an integer between 0 and 4.
24. A process as claimed in claim 23, wherein x is 2.
25. A process as claimed in any of claims I to 24, wherein 3 w + x 6.
26. A process as claimed in claim 25, wherein w + x = 4.
27. A process as claimed in any of claims I to 26, wherein the metal complex is Pd(PPh3)4.
28. A process as claimed in any of claims I to 27, wherein the fullerene or fuilerene derivative is selected from C60, C70, C76, C78, and C84.
29. A process as claimed in claim 28, wherein the fullerene is C60.
30. A process as claimed in any of claims 1 to 29, wherein the first solvent is an aromatic hydrocarbon.
31. A process as claimed in claim 30, wherein the first solvent is toluene.
32. A process as claimed in any of claims 1 to 31, wherein the second solvent is an alcohol.
33. A process as claimed in claim 32, wherein the alcohol is isopropanol.
34. A process as claimed in any of claims I to 33, wherein the metal complex is substantially soluble in the first solvent.
35. A process as claimed in any of claims I to 34, wherein the metal complex is substantially insoluble in the second solvent.
36. A process as claimed in any of claims 1 to 35, wherein the first and second solvents are substantially miscible.to
37. A process as claimed in any of claims I to 36, wherein a surfactant is added to the first and/or second solvent.
38. A process as claimed in any of claims 1 to 37, wherein the fullerene and/or fullerene derivative is combined with the first solvent prior to admixture with the metal complex and with the second solvent.
39. A process as claimed in claim 38, wherein the metal complex is combined with the first solvent prior to admixture with the second solvent.
40. A process as claimed in claim 38, wherein the metal complex is combined with the second solvent prior to the admixture of the first and second solvent.
41. A process as claimed in any of claims I to 37, wherein the metal complex is combined with the first solvent prior to admixture with the fullerene and/or fullerene derivative and with the second solvent.
42. A process as claimed in claim 41, wherein the fullerene and/or fullerene derivative is combined with the first solvent prior to admixture with the second solvent.
43. A process as claimed in any of claims 38 to 42, wherein the first solvent is added to the second solvent. -48 -44. A process as claimed in claim 43, wherein the first solvent is added drop-wise.45. A process as claimed in claim 43 or claim 44, wherein the first solvent is added to the second solvent at a rate of between 0.01 and 10 ml/min per ml of the second solvent.46. A process as claimed in any of claims 38 to 42, wherein the second solvent is added to the first solvent.47. A process as claimed in claim 46, wherein the second solvent is added drop-wise.48. A process as claimed in claim 46 or claim 47, wherein the second solvent is added to the first solvent at a rate of between 0.01 and 10 ml/min per ml of the first solvent.49. A process as claimed in any of claims 1 to 48, wherein the metal complex (a), the fullerene and/or fullerene derivative (b), and the first solvent (c) are in contact for less than 30 minutes prior to admixture with the second solvent.50. A process as claimed in any of claims 1 to 49, wherein all four components (a)-(d) are mixed substantially simultaneously.51. A process as claimed in any of claims I to 49, wherein the process is a continuous process for the preparation of fullerites.52. A process as claimed in any of claims I to 51, wherein a mole ratio of the metal complex (a) to the fullerene and/or fullerene derivative (b) of between 1:10,000 and 1:1 is used.53. A process as claimed in claim 52, wherein a mole ratio of the metal complex (a) to the fullerene and/or fullerene derivative (b) of about 1:19 is used.-49 - 54. A process as claimed in any of claims I to 53, wherein said process is performed under an inert atmosphere.55. A process as claimed in any of claims I to 54, wherein said process further comprises the step of removing the supernatant after fullerite precipitation.56. A process as claimed in claim 55, wherein said supernatant is removed by filtration.57. A process for the preparation of particles of ML', wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein y is an integer between 0 and 9, wherein said process comprises a process as claimed in any of claims I to 56.58. A process as claimed in claim 57, wherein said process is for the preparation of particles of the metal M. 59. A process as claimed in claim 57 or claim 58, wherein said process further comprises the step of dissolving the fullerite after precipitation to isolate the particles of ML' or M. 60. A fullerite preparable according to a process as claimed in any of claims 1 to 56.61. A fullerite comprising MLtX complexed to one or more fullerenes and/or fullerene derivatives, wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein x is an integer between 0 and 8, and wherein said fullerite does not comprise a faceted end.-50 - 62. A fullerite as claimed in claim 61, wherein the end surface of said fullerite is substantially perpendicular relative to the longitudinal axis of the fullerite.63. A fullerite as claimed in claim 61 or claim 62, wherein the end surface of said fullerite is substantially planar.64. A fullerite comprising ML'. complexed to one or more fullerenes and/or fullerene derivatives, wherein said fullerite further comprises particles of ML' on the surface of said fullerite, wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein x is an integer between 0 and 8, and wherein y is an integer between 0 and 9.65. A fullerite as claimed in claim 64, wherein said particles are approximately spherical.66. A fullerite as claimed in any of claims 64 to 65, wherein said particles have an average diameter of between 0.1 and 100 nm.67. A fullerite as claimed in claim 66, wherein said particles have an average diameter of between 0.5 and 20 nm.68. A fullerite as claimed in claim 67, wherein said particles have an average diameter of between I and 6 nm.69. A fullerite as claimed in any of claims 64 to 68, wherein y is an integer between 0 and 4.70. A fullerite as claimed in claim 69, wherein y is 0.71. A fullerite as claimed in any of claims 64 to 70, wherein said fullerite does not comprise a faceted end.72. A fullerite as claimed in claim 71, wherein the end surface of said fullerite is substantially perpendicular relative to the longitudinal axis of the fullerite.73. A fullerite as claimed in claim 71 or claim 72, wherein the end surface of said fullerite is substantially planar.74. A fullerite as claimed in any of claims 61 to 73, wherein M is a group 2 or a transition metal.75. A fullerite as claimed in claim 74, wherein M is selected from a transition metal of groups 8 to 10.76. A fullerite as claimed in claim 75, wherein M is selected from Ni, Pd or Pt.77. A fullerite as claimed in claim 76, wherein M is Pd.78. A fullerite as claimed in any of claims 61 to 77, wherein the oxidation state of M in ML'X and/or ML' is between (0) and (\TJJ).79. A fullerite as claimed in claim 78, wherein the oxidation state of M in ML'X and/or ML' is between (0) and (IV).80. A fullerite as claimed in claim 79, wherein the oxidation state of M in ML'X and/or ML' is (0).81. A fullerite as claimed in any of claims 61 to 80, wherein M is Pd(0).82. A fullerite as claimed in any of claims 61 to 81, wherein each L' is a monodentate ligand.83. A fullerite as claimed in any of claims 61 to 82, wherein each L' is the same.-52 - 84. A fullerite as claimed in any of claims 61 to 83, wherein each L is PPh3.85. A fullerite as claimed in any of claims 61 to 84, wherein x is an integer between 0 and 4.86. A fullerite as claimed in claim 85, wherein x is 2.87. A fullerite as claimed in any of claims 61 to 86, wherein the one or more fullerenes and/or fullerene derivatives are selected from C60, C70, C76, C78, and C84.88. A fullerite as claimed in claim 87, wherein the one or more fullerenes are C60.89. A fullerite as claimed in any of claims 61 to 88, wherein ML'X is complexed to the one or more fullerenes and/or fullerene derivatives via a 12-bond.90. A fullerite as claimed in claim 89, wherein said 2-bond is positioned across a bond forming one edge of both a 5-and a 6-membered ring of said fullerene or fullerene derivative.91. A fullerite as claimed in any of claims 61 to 90, wherein each ML'X is complexed to a single fullerene or fullerene derivative.92. A fullerite as claimed in any of claims 61 to 91, wherein each fullerene or fullerene derivative that is complexed to ML'X is complexed to a single ML'X.93. A fullerite as claimed in any of claims 61 to 92, comprising (2-C60)Pd(PPh3)2.94. A fullerite as claimed in any of claims 61 to 93, wherein 50 to 99.99% by weight of the fullerite consists of fullerenes and/or fullerene derivatives not directly complexed to MLIX.95. A fullerite as claimed in claim 94, wherein about 95% by weight of the fullerite consists of fullerenes and/or fullerene derivatives not directly complexed to ML'X.96. A fullerite as claimed in any of claims 61 to 95, wherein the crystal structure of the fullerite is substantially close packed.97. A fullerite as claimed in claim 96, wherein the crystal structure of the fullerite is substantially face-centred cubic. t098. A fullerite as claimed in any of claims 61 to 97, wherein the fullerite further comprises clusters on the surface of said fullerite, said clusters comprising one or more fullerenes and/or fullerene derivatives.99. A fullerite as claimed in claim 98, wherein said clusters have an average diameter of between 10 and 250 nm.100. A fullerite as claimed in any of claims 61 to 99, wherein said fullerite has a length of between 0.5 and 10 p.m.101. A fullerite as claimed in any of claims 61 to 100, wherein said fullerite has an average diameter of between 0.1 and 5 p.m.102. A process for the preparation of particles of ML! wherein M is a non-group 1 metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, and wherein y is an integer between 0 and 9, said process comprising the step of dissolving a fullerite as claimed in claim 60, or as claimed in any of claims 64 to 73, or as claimed in any of claims 74 to 101 when dependent from any of claims 64 to 73, in a solvent to isolate the particles of ML'.103. A process as claimed in claim 102, wherein said process is for the preparation of particles of the metal M. 104. A particle of ML' preparable according to a process as claimed in any of claims 57, 59 or 102.105. A particle of the metal M preparable according to a process as claimed in any of claims 58,59 or 103.106. A particle of ML' wherein M is a non-group I metal, wherein each L' is a ligand, each of which may be the same or different, wherein independently and optionally any two or more such ligands may together form a polydentate ligand, wherein y is an integer between 0 and 9, and wherein said particle has an average diameter of between 0.1 and 100 nm.107. A particle as claimed in claim 106, wherein said particle has an average diameter of between 0.5 and 20 nm.108. A particle as claimed in claim 107, wherein said particle has an average diameter of between I and 6 nm.109. A particle as claimed in any of claims 106 to 108, wherein ML'is the metal M. 110. A process for embedding particles as claimed in any of claims 104 to 109 in a matrix, said process comprising forming the matrix around a fullerite as claimed in claim 60, or as claimed in any of claims 64 to 73, or as claimed in any of claims 74 to 101 when dependent from any of claims 64 to 73.111. A process as claimed in claim 110, wherein said matrix comprises a polymer or a metal with the proviso that if the particles are metal and the matrix comprises metal, then the metal of the matrix is different to the metal of the particles.112. A process as claimed in claim 110 or claim 111, wherein said process further comprises a second step of dissolving the fullerite in a solvent to leave said particles embedded in an internal or external surface of said matrix.113. A process as claimed in claim 112, wherein said process further comprises a third step of etching the internal and/or external surface of said matrix to leave said particles affixed to but proud of the surface of said matrix.114. A matrix with particles affixed thereto, preparable by a process according to any of claims 110 to 113.115. A matrix comprising particles as claimed in any of claims 104 to 109 affixed thereto, wherein said matrix comprises a polymer or a metal with the proviso that if the particles are metal and the matrix comprises metal, then the metal of the matrix is different to the metal of the particles.116. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, as a catalyst.117. The use of claim 116, wherein said catalyst is a catalyst for reduction.118. The use of claim 117, wherein said catalyst is a catalyst for hydrogenation.119. The use of claim 116, wherein said catalyst is a catalyst for oxidation.120. The use of claim 116, wherein said catalyst is a catalyst for carbon-carbon bond formation.121. The use of any of claims 116 to 120, wherein said catalyst is used in heterogeneous catalysis.122. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, in the formation of carbon nanostructures.123. A process for the synthesis of carbon nanostructures, said process comprising heating a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, in the presence of a carbon-containing gas.124. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, in an electronic application.125. The use of claim 124, wherein said electronic application is an electrode, a semi-conductor, a transistor, an optical device, a solar cell, a light source such as a light emitting diode, a photodetector, or a data storage device.126. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, as an adsorbent or a membrane.127. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, in a fuel cell.128. Use of a fullerite as claimed in any of claims 60 to 101, a particle as claimed in any of claims 104 to 109, or a matrix as claimed in claim 114 or 115, in a magnetic or electromagnetic application.129. The use of claim 128, wherein said magnetic or electromagnetic application is a data storage device.130. A process, use, particle, matrix or fullerite as substantially described or illustrated herein.