Patent Application: US-4925900-A

Abstract:
a compound consists of a fractal - like , plain or organometallic array useful for energy storage devices . a dendrimer useful in the synthesis of the fractal - like compound includes a single ligating moiety bound to a surface of each quadrant of the dendrimer . a method of making metallo - based molecules includes the steps of combining monomers selected from the group consisting of bipyridal - and terpyridal - based ligands with connecting metals and self assembling macrocycles wherein the monomes are interconnected by the metals .

Description:
generally , the present invention provides several generic concepts and several further specific compounds and methods of making compounds , all in combination significantly advancing the art of electrolyte and electrocomponents in solid state , energy storage devices . the methods disclosed below are useful for manufacturing either monomers used as building blocks to create compounds or the compounds per se , which are useful as electrolytes in energy storage devices . such compounds useful in energy storage devices are capable of encapsulating , entraining , and stabilizing metal and non - metal nanoclusters for use in electromaterials and surfaces . such materials , by use of combinatorial - based synthetic techniques , are disclosed herein which allow for the preparation and rapid testing of heterogeneously functionalized branched assemblies with tunable physiochemical properties . such tunable physiochemical properties allow for the maximization of enhanced electrolyte capability of stackable compounds capable of energy storage and release through the metals retained thereby . while numerous routes and electrolyte architectures can be envisioned , four approaches are described which allow access to these materials . more specifically , dendritic polymer - based electrolyte materials , as shown in fig1 , are predicated on the use of the process for construction of all - saturated hydrocarbon dendrimers ( newkome et al ., u . s . pat . no . 5 , 154 , 853 , 1992 ; newkome et al ., unimolecular micelles , angvew . chem ., int . ed . engl ., 1991 ; newkome et al ., alkane cascade is polymers possessing micellar topology : micellanoic acid derivatives , angew . chem ., int . ed . engl . 1991 ) ( i . e ., 14 and 15 that are prepared from monomers 12 and 13 via sequential alkylation , reduction , and halogenation ) and the attachment of polyethylene glycol units on the dendrimer surface . polyethylene glycol ( peg ) units can be easily attached to dendrimers and building blocks via the well established williamson synthesis ( buckmann et al ., 1981 ; burns et al ., 1999 ) to afford peg - modified dendrimers ( 16 ). examination of these materials in concert with added “ free ” salts ( lipkowski et al ., 1994 ; owen , j . r ., 1997 ; salomon , m ., 1998 ; cisak et al ., 1993 ) [ e . g ., lic10 4 , licf 3 so 2 , lipf 6 , lin ( so 2 cf 3 ) 2 , and lic ( so 2 cf 3 ) 3 ] is planned . peg commercial availability allows access to a variety of chain lengths . saturated hydrocarbon frameworks are effectively inert towards oxidizing and reducing conditions . hence , it is expected that improved electrolyte stability , more efficient li - ion transport , and decreased electrolyte layer thickness will result in greater specific energy , energy density , and battery cycle life . ( owen , j . r ., 1997 ) specific present pitfalls ( lipkowski et al ., 1994 ) addressed by this technology are ( a ) stability towards highly oxidizing and reducing environments [ i . e ., at the anode and cathode interfaces due to the absence of reactive functional groups such as nh , oh , etc . ]; ( b ) electrolyte crystallinity and brittleness [ i . e ., such as found with lil and some other polymeric matrices ]; ( c ) mechanical strength ; ( d ) charge and discharge temperature range operation ; ( e ) electrolyte layer thickness [ inter - electrode gaps corresponding to ˜ 10 − 8 to 10 − 9 m are envisioned assuming a dendrimer radius of 20 – 25 å ]; ( f ) lithium plating [‘ dendrite ’ formation should be reduced in a more electrochemically stable electrolyte region ]; and ( f ) safety [ environmental as well as operational ]. synthesis of branched peg architectures is shown in fig2 . monomers allowing for attachment of the polyether moieties to a wide array of surfaces and preconstructed dendrimers are prepared by employing the branched monomer design and isocyanate technology . ( newkome et al ., isocyanate - based dendritic building blocks : combinatorial tier construction and macromolecular property modification , angew . chem ., int . ed . engl . 1998 ; newkome et al ., designed monomers and polymers , 1997 ; newkome et al ., u . s . pat . no . 5 , 773 , 551 , 1998 ) for example , monomethylated triethylene glycol ( 17 : prepared via reaction of the glycol with 1 equivalent of mel ) can be reacted with the known nitrotrichloride ( 18 ) ( newkome et al ., synthesis , 1991 ) to give the nitrotris ( triethylene glycol ) ( not shown ) that can be reduced to afford the corresponding amine 19 . treatment of this amine with phosgene ( or a phosgene equivalent such as di - or triphosgene ) yields isocyanate 20 . a second generation dendron can be accessed via coupling of amine 19 with nitrotris ( acid chloride ) 21 . subsequent reduction of the nitro moiety and treatment with phosgene gives an isocyanate monomer possessing 9 peg units ( 22 ). tritethylene glycol units were prepared possessing terminally modified , complementary reactive and inert moieties ( fig3 ). triethylene glycol was reacted separately with ethyl diazoacetate and benzyl chloride to afford ester 23 and benzyl ether 24 , respectively . the free hydroxyl group of monofunctionalized glyco ( 23 ) was then converted to the corresponding amine via established procedures . thus treatment of alcohol 23 sequentially with mesyl chloride ( msc1 ) and sodium azide ( nan 3 ) followed by catalytic hydrogenation ( pd — c , h 2 ) yielded amine 25 . peg - based dendrimers , possessing polyether units throughout the dendritic structure , are accessible via use of these modified polyethers . for example transforming alcohol 24 to the 1 → 3 branched monomer 27 via conversion of 24 to the mesylate and reaction triol 26 ( obtained by reduction of the corresponding tetraacid followed by treatment with one equivalent of acetyl chloride ; a monosubstituted pentaerythritol can also be employed ). reaction of the same mesylate with pentaerythritol followed by reductive debenzylation should yield core 28 . basic deprotection of the acetyl moiety on monomer 27 , transformation to the mesylate , and attachment to tetraol 28 provides the first tier polyether dendrimer 29 . repetition of the sequence allows access to higher generations . in a complementary scheme , peg - based dendrimer 18 is constructed using amide - based monomer connectivity . amide versus ester based connectivity was chosen due to the greater stability of the c ( o )— n bond . thus , coupling aminoester 25 with nitrotris ( acid chloride ) 21 and subsequently reducing the nitro group should afford aminotriester 31 . the corresponding core 32 can then be accessed by reaction of the traacid 30 with four equivalents of amino 25 . selective ester hydrolysis of core 32 followed by coupling of monomer 31 is anticipated to yield the first generation dendrimer 33 . based on the high yields ( generally 80 – 90 %) of the reactions to access the building blocks and dendrimers in scheme 3 and the commercial availability of diverse polyethylene glycol homologs , a wide latitude in structural design is attainable . in view of the above , the present invention provides novel peg dendrimer frameworks and methods of making the same . it should be noted that such methods can be utilized in homologous synthesis ; that is , such methods can be utilized to synthesize homologues by modifications of a method well known in the art . further , the above methods demonstrate the ability of the present invention to produce a wide array of surfaces and preconstructed dendrimers employing branched monomer design and isocyanate technology developed by applicants . such compounds can have a flat architecture capable of stacking , such being inert towards oxidizing and reducing conditions . thus , they can provide improved electrolyte stability and more efficient li - ion transport and decreased electrolyte layer thickness . this results in greater specific energy , energy density , and battery cycle life , as demonstrated by the prior art discussed above . the present invention further provides combinatorial methods utilized toward the synthesis of multiple unit positioning . while intra - and inter - molecular “ multiple structural element positioning ” is in its infancy , foundations rooted in such areas as molecular recognition and other non - covalent interactions suggest a host of potential architectures . for example , structural units can be held in precise juxtaposition via rigid control units ( zhang et al ., 1992 ; zhang et al ., 1994 ) that bind branched units via h - bond - based molecular recognition ( newkome et al ., chem . commun ., 1996 ) or , more simplistically , an ‘ event ’ ( chemical or physical ) can be effected via absorption of molecular guests that fill internal void regions and cause branch chain movement . a simple analogy is found in well known polymer swelling . competition for binding sites and compartments can form the basis for “ molecular triggers .” additionally , a fundamental property of branched macromolecules that is useful for the construction of “ next generation ” materials is revealed via consideration of the allowed bond rotations ( torsions ) within these structures . ( newkome et al ., combinatorial chem ., 1999 , in press ) this suggests molecular surfaces that are “ dynamic ” whereby terminal units can at one instant be separated as far as physically possible and in another moment these same units are nearest adjacent neighbors . essentially , movement of terminal groups or units about the surface of the branched superstructure is predicated on simple bond rotations which can be effected by “ logical constants .” this dynamic property , which conceptually imparts a “ rubik &# 39 ; s sphere ” character to these unique molecules , can be controlled by the use of logical constraints ( i . e ., site - specific molecular recognition , disruption of internal h - bonding , swelling in void regions , etc .) to facilitate construction of macromolecular assemblies with controllable functional unit positions . “ combinatorially ” prepared structures ( newkome et al ., isocyanate - based dendritic building blocks : combinatorial tier construction and macromolecular property modification , angew chem ., int . ed . engl ., 1998 ; newkome et al ., combinatorial chem ., 1999 ) whereby tiers are constructed by using a mixture of equally reactive , complementary monomers are integral elements for the ultimate construction of tunable networks . as proof of the concept that branched architectures are dynamic with respect to functional group position , a dendrimer was constructed with a single ligating moiety bound to the surface of each quadrant of a dendrimer prepared using a tetravalent core . the key monomer 36 possessing a single bipyridine unit can be accessed via standard reactions ( fig4 ). starting with 4 - nitrobutyric acid ( 34 ), the bipyridyl diester 35 can be afforded by coupling of the aminobipyridine unit ( newkome et al ., j . org . chem . 1997 ) followed by michael - type addition of tert - butyl acrylate and nitro moiety reduction . ( dominguez et al ., 1961 ) amine acylation of 35 ( dcc ) addition of methyl acrylate , methyl ester deprotection ( mcmurray , j ., 1976 ) ( nacn , dmf ), and coupling ( dcc ) of the aminotriester precursor to 6 with subsequent reduction of the nitro group to an amine ( weis et al ., 1995 ) affords the desired homologated aminobipyridine 36 . acylation of four equivalents of 36 with tetraacyl chloride 37 yields dendrimer 38 ( fig5 ; the fourth bipyridine is not depicted ), whereupon metal addition ( issberner et al ., 1997 ) ( e . g . ruc1 3 , under reducing conditions ) in dilute solution the trisbipyridine metal complex [ e . g ., ru ( ii )] 39 is expected . other ligating species can be envisioned to function analogously , such as the siderophore - based dihydroxybenzene . ( tor et al ., 1987 ) standard analyses using uv , nmr , and mass spectrometry techniques are expected to confirm the presence of one free bipyridine and three complexed ligands . the structural proof - of - concept , for the rubik &# 39 ; s sphere model , ( tor et al ., 1987 ) although synthetically lengthy , is critical to the demonstration that randomly placed functionalities on a dendron , sphere , or surface can contact , influence , or affect each other . the “ rubik &# 39 ; s sphere concept has far reaching ramifications related to the incorporation of dendritic monomers that can rotate to favorable orientations to stabilize metals , clusters , and composites . in view of the above , the present invention provides a monomer useful in the construction of dendrimers for investigating macromolecular torsional behavior . such torsional behavior of branch architectures which are capable of being dynamic with respect to functional positioning groups . such rotatable dendritic monomers capable of stabilizing metals , clusters and composites are used as “ switches ” for transferring ions or controlling ion transfer . control can be obtained by the use of changing environments wherein the environment itself , whether hydrophobic and hydrophilic , high ioninicity , low ioninicity , etc . can induce torsional changes which result in bringing ions or the like into or out of proximity with each other thereby able to either transfer or not transfer ionic moieties . hence , the present invention provides significant utility in the molecular or electronics field . likewise , such “ rubick &# 39 ; s ” sphere capability is useful in electrodes and solid state electronics . the present invention further provides means for making novel nanoscale metallomacrocycles . as part of efforts to develop nanoscale and molecular - sized energy storage devices , the potential self - assembly of polymetallic architectures for energy collection was investigated . these macrocycles are the first in a series of unique fractal polymers capable of molecular stacking and metal positioning . synthesis of these novel materials is illustrated in fig6 whereby a hexaruthenium ring is targeted . beginning with the known dialdehyde 40 the primary bisterpyridine building block 41 was crafted via treatment with 2 - acetylpyridine followed by reaction with nh 4 oac . hexa - metallo ring 42 can then be accessed by a simple , one step , high yield , self - assembly of bisterpyridine 41 and six equivalents of ruc1 3 . hn 2 o in the presence of n - ethylmorpholine . ruthenium connectivity was initially employed to prove the self - assembly process but other metals work in a comparable fashion . also , rigid structural control facilitates the introduction of alternating metals . as well , 1 , 3 , 5 - versus 2 , 4 , 6 - external substituents can be incorporated , in a precise manner , affording a series of architecturally related materials . different sized rings ( 43 – 45 : fig7 ) and derivatization of the peripheral methyl moieties via free radical halogenation ( newkome et al ., synthesis , 1984 ) and susuki - type coupling ( xu et al ., stiff dendritic macromolecules : extending small organic chemistry to the nonoscale regime , polym . prep ., 1993 ; xu et al ., synthesis and characterization of a high molecular weight stiff dendrimer , angew . chem ., int . ed . engl ., 1993 ) of rigid or flexible appendages to facilitate “ network ” positioning of the poly - metal centers were investigated . for example , the branch modified structure 46 , which is easily accessed via attachment of known , pre - formed polyphenylacetylene dendrons , ( xu et al ., 1994 ) possesses structural requirements known to promote columnar mesophase ( 47 ) formation ( markovitsi et al ., 1988 ) ( i . e ., near planarity and lipophilic arms positioned in a symmetrical cyclic array ). further , the phenylacetylene dendritic arms act as “ molecular antennas ,” as reported in the literature , ( kopelman et al ., 1998 ; shortreed et al ., 1997 ; xu et al ., 1994 ) for energy direction and concentration towards the electron - poor poly - metallic rings . interestingly , stacked assemblies using anionic - terminated , hydrocarbon dendrimers as counter ions and “ insulators ” suggest their use in a number of areas of molecular electronics ( i . e ., leds , photodiodes , and thin film transistors ) due to the potential to form alternating conducting and non - conducting layers . ( luryi et al ., 1999 ; krummenacker et al ., 1995 ; barnes et al ., 1999 ) although the first members of this series are depicted in fig5 , the creation of higher generations via the incorporation of additional terpyridine moieties can also be accomplished ( 48 ; fig8 ). in view of the above , the present invention provides compounds consisting of fractal - like , planar organometallic arrays . the term “ fractal ” is used in its accepted meaning , fractal geometry being concerned with the quantitative description of complex structures and the way in which the structures transform under a change of lens scales . the most simple fractals are self - similar or scale invariant structures that are invariant to an isotropic change of length scales . that is , they “ look the same ” under different magnifications . familiar examples of such fractals are coastlines , clouds , and biological structures , such as the vascular system and nerve cells . during the past few years , these ideas have become widely disseminated and apply to a very broad range of materials and phenomena . the fractals of the present invention provide for stackable , is planar organometallic arrays , especially in higher generations of the fractals , capable of encapsulating , entraining , and stabilizing metal and non - metal nanoclusters for use as stacked electrode materials . the fractals , as well as the previously disclosed dendrimers can be utilized in combination with various metals having the appropriate ionic properties for use in energy collection and storage devices . examples of such metals , are cu , fe , ru , os , zn , co , ni , mn , pd , pt , rh , re , w , ir , au , and ag . use of dendritic chemistry for the creation of new and improved anode and cathode materials is provided herein . both “ lithium ”- and “ lithium - rocking - chair ”- type electrodes are targeted . dendritic “ void volume ” employed in concert with internal and external metal or non - metal coordination sites as well as aqueous and non - aqueous chemical equilibria provide a wide range of options for their construction . essentially , the unique , branched architecture of dendrimers simply provide a molecular - sized reaction vessel for component polymerization or colloidal stabilization and solubilization . polymerization and particle stabilization using micelles and vesicles are well known . ( fendler et al ., 1975 ; fendler et al ., 1994 ) metal coordination to the interior of dendritic framework has been demonstrated in labs employing alkyne , ( newkome et al ., unimolecular micelles , angew . chem ., int . ed . eng ., 1991 ; newkome et al ., alkane cascade polymers possessing micellar topology : micellanoic acid derivatives , angew . chem ., int ed . engl ., 1991 ; newkome et al ., chemistry within a unimolecular micelle precursor : boron superclusters by site - and depth specific transformations of dendrimers , angew . chem ., 1994 ; newkome et al ., chemistry within a unimolecular micelle precursor : boron superclusters by site - and depth - specific transformations of dendrimers , angew . chem ., int . ed . engl ., 1994 ) bipyridine , ( newkome et al ., synthesis of unsymmetrical 5 , 5 ′- disubstituted 2 , 2 ′- bipyridines , j . org . chem ., 1997 ; newkome et al ., cascade infrastructure modification via integration of application - based monomers , polym . mater . sci . eng ., 1995 ; newkome et al ., design , syntheses , complexation , and electrochemistry of polynuclear metallodendrimers possessing internal metal binding loci , chem . eur . j ., 1999 ) and terpyridine moeities , ( newkome et al ., electroactive metallomacromolecules via tetrabis ( 2 , 2 ′: 6 ′ 2 ″- terpyridine ) ruthenium ( ii ) complexes : dendritic networks towards constitutional isomers and neutral species without external counterions , chem . commun ., 1998 ; newkome et al ., neutral highly branched metallomacromolecules : incorporation of ( 2 , 2 ′: 6 ′ 2 ″- terpyridine ) ruthenium ( ii ) complex without external counterions , chem . commun ., 1999 ; 1 newkome et al ., construction of dendritic assemblies : a tailored approach to isomeric metallomacromolecules by means of bis ( 2 , 2 ′: 6 ′ 2 ″- terpyridine ) ruthenium ( ii ) connectivity , macromolecules , 1998 ) while coordination and subsequent reaction have produced “ nanoparticles ” ( i . e ., zero valent pt clusters [ zhao et al ., dendrimer - encapsulated pt nanoparticles : synthesis , characterization , and applications to catalysis , adv . mater . ( weinhem , fed . repub . ger . ), 1999 ; chechik et al ., 1999 ; zhao et al ., homogeneous hydrogenation catalysis with monodisperse , dendrimer - encapsulated pd and pt nanoparticles , angew . chem . int ed ., 1999 ] and cus 2 [ balogh et al ., 1998 ; tan et al ., 1999 ; dagani , r ., 1999 ]). dendrimers can be used as templates ( 49 ; fig9 ) for the preparation of uniform , nanocrystallite materials such as hydrous ruo 2 , ( ru — ti ) o x ( kriesel et al ., 1999 ; long et al ., 1999 ) and organic - based binary material such as polyethyleneoxide - dihydrophenazine block copolymer . ( tran et al ., 1998 ) use of dendrimers for construction of nonocrystallites for electrode materials allows for high surface area and near uniform dimensions thereby enhancing electrode stability , conductivity , and capacity . the concept of dendrimer nanocrystallite formation is predicated on the preparation of semiconductor crystallites via “ arrested precipitation ” techniques , or templated polymerization , using structured reaction media such as zeolites , ionomers , porous glass , vesicles , micelles , and gels . ( steigerwald et al ., 1990 ) more recently , cds clusters have been derivatized with pyridine units and fabricated into superarrays , ( steigerwald , et al ., semiconductor crystallites : a clas of large molecules , acc . chem . res ., 1990 ) and superlattices , ( que et al ., 1988 ; que et al ., 1990 ) thus electronically coupling the individual clusters for enhanced luminescence emission properties . thus , use of the “ void volume ” inherent in dendritic assemblies and components affords an ideal method for preparation of crystallites with a high degree of purity and monodispersity , as well as at sizes relevant to the “ quantum effect ” ( i . e ., 50 å or less ). ( que et al ., 1988 ; que et al ., 1990 ; weller , h ., 1993 ) in view of the above , the present invention most generally provides a dendrimer nanocrystallite . the present invention further provides a method of preparing polyterpyridyl ligands in a self - assembling manner . by “ self - assembling ” it is meant that the combination of the components will , without further chemical or physical prompting assemble into a higher order ( fractal ) architecture . more specifically , the present invention provides a preparation of a bis ( terpyridine ) monomer possessing a 120 ° concave angle with respect to the two ligating moieties . this would facilitate the assembly of six building blocks with six connecting metals in the ubiquitous benzenoid architecture . the potential to synthesize such constructs , with little equilibration ( metal - ligand exchange ) under mild physiochemical conditions , is predicated on the unique strength of the terpyridine - ru coordination . synthesis of the requisite building block began via treatment of the known dialdehyde ( 28 ) 1 ( fig9 ) with ecess 2 - acetylpyridine ( 29 ) followed by nh 4 oac to afford ( 66 %) of the desired angular ( 1200 ) bis ( terpyridine ) 2 . confirmation of this structure included 1 h nmr absorptions at 7 . 38 ( dd ; 5 , 5 ″), 7 . 82 ( s ; 4 , 6 ar ), and 8 . 83 ppm ( s ; 3 ′, 5 ′) reaction of hexagonal precursor 2 with two equivalents of rucl 3 - nh 2 o produced the minimally soluble , paramagnetic bis [ ru ( iii )] adduct 7 ( fig1 ) which was treated without further purification with one equivalent of monomer 2 under reducing conditions ( n - ethylmorpholine ) to yield ( 85 %) the self - assembled , diamagnetic , hexameric ru ( ii ) complex 8 ( table 1 ). the 1 h nmr spectrum ( fig1 ) of the purified material revealed a single absorption at 2 . 90 ppm ( ch 3 ) suggesting the presence of only one type of monomeric unit in contrast to that expected for a linear oligomer . other diagnostic spectral attributes ( 1 h nmr ) included upfield and downfield shifts , respectively , of the 6 , 6 ″ signals ( δ7 . 62 ; δδ1 . 13 ) and the 3 ′, 5 ′ signals ( δ9 . 37 ; δδ0 . 54 ). cosy and hetcor spectra of the bis ( ligand ) and the self - assembled macrocycle verified the peak assignments and coupling patterns . hexamer 8 , isolated as the 12 cl ′ salt , exhibited solubility in meoh and hot h 2 o while conversion to the 12 pf 6 − facilitated solubilization in acetonitrile , acetone , and dimethylsulfoxide . in order to ensure structural verification of macrocycle 8 , a stepwise , directed route to the material was devised . initially , further characterization of the key monomer 2 , as well as the bis ( terpyridyl )- ru ( ii ) connective moieties , was provided by the formation of the mono - and di - ru ( ii ) complexes 3 and 5 ( fig9 ). reaction of 4 ′-( 4 - methylphenyl )- 2 , 2 ′: 6 ′, 2 ″- terpyridine ( 30 ) with rucl 3 - nh 2 o followed by addition of the unmetallated mono - and di - terpyridine ligands ( 4 and 2 , respectively ) afforded the desired complexes . as in the case of hexamer 8 , constructs 3 and 5 exhibited a downfield shift ( 1 h nmr ) of the 3 ′, 5 ′ proton resonances ( δ9 . 20 ; δδ0 . 46 ) and an upfield shift of the 6 , 6 ″ signals ( δ7 . 62 ; δδ1 . 07 ). bis ( ru ) complex 5 was also prepared employing ligand 7 followed by capping with the free monoterpyridine precursor to 4 . subsequently , the diamagnetic tris ( oligomer ) 6 was prepared from building block 2 via sequential treatment with two equivalents of rucl 3 - nh 2 o and then unmetallated monomer 2 . the 1 h nmr spectrum of trimer 6 showed a complex pattern of broadened absorptions in the aromatic region ( δ9 . 76 – 7 . 40 ) as well as the two anticipated singlets arising from the non - equivalent methyl groups ( δ2 . 79 , 3h , 2 . 94 , 6h ). finally , reaction of the oligomer 6 with one equivalent of its bis [ terminal ru ( iii )] adduct yielded a material possessing identical spectral and physical characteristics to that of the self - assembled hexamer 8 . notablyu , a silica tlc of the macrocycle 8 , eluting with a mixture of ch 3 cn and aqueous kno 3 , clearly showed the absence of any starting materials , while the uv spectrum extinction coefficients ( e ) exhibited a 5 . 1 , 5 . 5 , and 5 . 8 fold increase for λ max at 290 , 312 and 496 nm , respectively ( table 2 ), when compared to analogous measured coefficients for the monoru ( ii ) complex 3 . an electron micrograph ( em ) of 8 + 12 ( 12 pf 6 ) revealed a regular , packing morphology with particle sizes ranging from ≡ 160 to 350 å ( fig1 a ) while powder x - ray diffraction showed only short - range order with determined d - spacings at 7 . 99 , 6 . 24 , and 4 . 32 å . powder diffraction spectra of bis [ ru ( ii )] complex 5 exhibited a similar pattern ( d - spacings ; 10 . 11 , 7 . 58 , 5 . 80 and 4 . 32 å ). molecular modeling of macrocycle 8 ( fig1 b ) indicated a diameter of 37 . 5 å , a minimum inner void distance of 17 . 5 å and a distance between adjacent ru metals of 13 . 5 å . in an effort to modify the generally poor solubility of macrocycle 8 , as well as provide organizational scaffolding for non - bonded network formation , the counter ions in 8 + 12 ( 12 cl ) were exchanged with a dodecarboxylate - terminated dendrimer ( 31 ) to give 8 + 12 [ c ( ch 2 och 2 ch 2 conhc ( ch 2 ch 2 co 2 −) 3 ) 4 ], which is an extremely insoluble assembly . however , a 1 : 1 mixture of hexamer 8 and a third generation carboxylate - terminated dendrimer gave 8 + 12 ( g3 - 108 - co 2 − ), which produced a deep red d 2 o solution ( 25 ° c .) allowing verification of aqueous solubility via 1 h nmr . the use of compact , charge concentrated , ( psuedo ) spherical dendrimers possessing uniquely positioned anionic counterion character affords a convenient circumvention of the spatial randomness of traditional simple counterions in such complexes . these results have led to the construction of heteroleptic macrocycles . bromo analogs of monomethyl terpyridine 2 and the p - methyl monoterpyridine 4 were prepared starting with 5 - bromo - m - xylene or 4 - bromobenzaldehyde , respectively . reaction of the bromomonoterpyridyl ligand ( not depicted ) with ru ( iii ) adduct 4 gave the anticipated ru ( ii ) complex 9 exhibiting nearly identical 1 h and 13 c nmr spectra to that of complex 3 . while addition of the bromo building block 10 to the bis [ ru ( ii )] adduct 7 afforded the mixed monomer macrocycle 11 . evidence for its formation includes a symmetrically similar yet expectedly broadened 1 h nmr spectrum corresponding exactly to that of the hexamethyl analog 8 . hetcor experiments further support the structure . in conclusion , the iterative synthetic method combined with fundamental properties of branched macromolecular architecture allows the realization of new materials to promote advances in energy storage devices and their components . construction of a modular set of building blocks or monomers is essential and key to the realization of the chemistry discussed herein . dendrimer - based electrolyte materials enhance solid state lithium - type batteries via improvements in such properties as electrode separation , electrolyte solubility , and ion conduction , and safety . operational temperature ranges increase due to better electrolyte solubility and matrix stability . improved anode and cathode materials to result via the potential for branched architectures to be employed for the preparation and stabilization of metal and non - metal colloids and composites . use branched architectures for binders in existing materials improve surface areas and retard polarization gradients thereby enhancing ion diffusion and overall conduction . metal encapsulation with branched architectures finds utility in many areas of battery technology and molecular electronics . ramifications include the ability to produce smaller particles with greater cumulative surface areas that ultimately facilitate better ion diffusion within is the electrode and at the electrode - electrolyte interface . use of dendritic vessels as molecular reactors , in a similar fashion as micelles are employed for polymerizations , allow the investigation of new organic - and organometallic - based copolymers and composites . the single - step construction of new fractal - like , planar organometallic arrays provides new methods of energy storage and conduction via the potential to precisely position metals within large networks . combinatorial methods of macromolecular construction are proposed that ultimately lead to the creation of single molecules possessing the capability of energy storage and release ( i . e ., molecular batteries ). creation of molecules with the capacity to take advantage of multiple environmental interactions at multiple sites within the superstructure provides vast opportunity for the examination and evaluation of materials related to energy storage devices . the overall unifying theme presented in this proposal relates to the melding of iterative synthetic protocols with more mature research arenas for the production of utilitarian materials . ultimate control of macromolecular structural features leads to ultimate control of macromolecular properties and thereby lead to tunable macroscopic material properties . throughout this application , various publications , including united states patents , are referenced by author and year and patents by number . full citations for the publications are listed below . the disclosures of these publications and patents in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains . the invention has been described in an illustrative manner , and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation . obviously , many modifications and variations of the present invention are possible in light of the above teachings . it is , therefore , to be understood that within the scope of the described invention , the invention may be practiced otherwise than as specifically described . newkome , g . r . ; moorefield , c . n . ; vogtle , f . dendrimers and dendrons : concepts , synthesis , applications ”, vch : weinheim , germany 2001 . hult , a . ; johansson , m . ; malmstrom , e . “ hyperbranched polymers ” in advances in polymer science : branched polymers ; springer - 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