Insight into the SBU condensation in mg coordination and supramolecular frameworks: a combined experimental and theoretical study

This work is to emphasize the influence of the synthetic procedures in the isolation of different coordination polymers that coexist under hydro-/solvothermal conditions. An experimental and theoretical study in the Mg(2+):4,4'-(hexafluoroisopropylidene)bis(benzoic acid):1,10-phenantroline system has been carried out. Computational studies have determined the relative energies for those compounds that coexist under certain hydrothermal conditions, and have helped to identify the driving forces for the formation of the different phases. The five new compounds belong to five different structural types: AEPF-14, which presents two polymorphs (α- and β-) ([Mg(H(2)O)(4)(phen)(2)]L), AEPF-15 ([Mg(HL)(2)(phen)]) and AEPF-16 ([Mg(H(2)O)(2)(L)(phen)]) are both 1D MOFs (AEPF-16 with a helical structure), and AEPF-17 ([Mg(H(2)O)(L)(phen)]) with a 2D structure. Hydrogen bond interactions found in the five compounds have been taken into account to study the topology of their supramolecular nets. Finally, dehydration studies performed on AEPF-14 (α- and β-) and AEPF-16 have shown that the topological type of their supramolecular networks determines the structural changes that take place during the dehydration processes of these Mg compounds.     

Crystal structure and magnetic properties of Gd2([18]crown-6)2(OH)2(CH3CN)2[Ni(dmit)2]4 complex having f- and pi-spins

Crystal structure and magnetic properties of Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2)[Ni(dmit)(2)](2) (dmit(2)(-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) are reported. Gd(3+) ions (S = (7)/(2)) were introduced into the pi-spin network of [Ni(dmit)(2)](-) (S = (1)/(2)) complex as a binuclear supramolecular cation, Gd(2)([18]crown-6)(2)(OH)(2)(CH(3)CN)(2), in which two Gd([18]crown-6) units are bridged with two hydroxide ions. The weak antiferromagnetic interactions between Gd.Gd through hydroxide ions were observed, and [Ni(dmit)(2)](-) formed isolated monomers and dimers in the crystal.     

Enclosure of a Keggin-type heteropolyoxometalate into a tubular π-space via hydrogen bonds with a nonplanar Mo(V)-porphyrin complex forming a supramolecular assembly

A 2:1 supramolecular assembly composed of a non-planar Mo(V)-porphyrin, [Mo(DPP)(O)(H(2)O)](+) (1) (DPP(2+); dodecaphenylporphyrin), and a Keggin-type heteropolyoxometalate (POM), α-[(n-butyl)(4)N](2)[SW(12)O(40)] (2), was formed via hydrogen bonds. The crystal structure was determined by X-ray crystallography to clarify that the POM was enclosed into a π-space of a supramolecular porphyrin nanotube by virtue of a hydrogen-bond network. In contrast to the formation of the 2:1 assembly ([{Mo(DPP)(O)(H(2)O)}(2)(SW(12)O(40))] (3)) between 1 and [SW(12)O(40)](2-) in the crystal, it was revealed that those two components form a 1:1 assembly in solution, in light of the results of MALDI-TOF-MS measurements in PhCN. Variable-temperature UV-vis spectroscopic titration allowed us to determine the thermodynamic parameters for the formation of the 1:1 supramolecular assembly in solution, the heat of formation (ΔH) and the entropy change (ΔS). These results provide the first thermodynamic data set to elucidate the formation process of supramolecuar structures emerged by hydrogen bonding between metalloporphyrin complexes and POMs, indicating that the formation of the assembly is an entropy-controlled process rather than an enthalpy-controlled one. Comparisons of the thermodynamic parameters with those of a planar Mo(V)-porphyrin complex also highlighted high Lewis acidity of the Mo(V) centre in the distorted porphyrin.     

Aurophilicity versus mercurophilicity: impact of d10-d10 metallophilic interactions on the structure of metal-rich supramolecular assemblies

Treatment of U-shaped, binuclear Cu(I) complexes 1,1' (1, counterion: BF(4)(-); 1', counterion: PF(6)(-)) with metal cyanide linear linkers K[Au(CN)(2)] (3) and Hg(CN)(2) (4) lead to formation of new supramolecular assemblies 5,5' and 6,6', respectively, in good yield. These derivatives have been characterized by NMR spectroscopy, IR, and X-ray diffraction studies. Derivative 5,5' are supramolecular metallacycles in which intramolecular aurophilic interactions between the Au(I) metal centers of the linkers are observed. Derivative 5 crystallizes as a single solid phase, whereas derivative 5' is characterized in the solid state as four different pseudo-polymorphs (5'a-d). Notably in the case of phase 5'd, a dimer of supramolecular metallacycles bounded by intermolecular aurophilic interactions is formed. Conversely, derivatives 6,6' present large structural diversity depending on the nature of the counterion. Derivative 6 is a supramolecular rectangle in which the Hg(II)-Hg(II) metal distance suggests mercurophilic interaction, whereas 6' crystallizes as two different pseudo-polymorphs 6'a,b, that is, a one-dimensional coordination polymer and one oligomer with no short Hg(II)-Hg(II) metal contacts, respectively. In derivatives 6,6', short contacts between the Hg(II) metal centers and fluorine atoms of the counterions are also observed, which may explain the counterion structural dependence of these supramolecular assemblies based on Hg(II) metal cyanide linker. Comparison of the different solid-state structures characterized highlights the importance of weak secondary interactions between the linkers for the formation supramolecular metallacycles from molecular clips 1,1' and suggests the range of energies required for these interactions to form metallacycles and to induce self-aggregation.     

Grid-type two-dimensional magnetic multinuclear metal complex: strands of ([CuII(mu-4,4'-bpy)]2+)n cross-linked by octacyanotungstate(V) ions

Reaction of the preorganized strands of ([Cu(II)(mu-4,4'-bpy)](2+))n (4,4'-bpy = 4,4'-bipyridine) with [W(V)(CN)(8)](3)(-) leads to a novel cyano-bridged Cu(II)(3)W(V)(2) complex [Cu(mu-4,4'-bpy)(DMF)(2)][Cu(mu-4,4'-bpy)(DMF)](2)[W(V)(CN)(8)](2).2DMF. 2H(2)O 1. The structure of 1 consists of the expected 2-dimensional grid-type network which is built of infinite ([Cu(II)(mu-4,4'-bpy)](2+))n chains cross-linked by octacyanotungstate units. The Cu(II)-NC-W(V)-CN-Cu(II) linkage exhibits the topology of a 3,2-chain. The skeleton of the layer is additionally stabilized by a hydrogen bond network formed by terminal cyano ligands of the [W(CN)(8)](3-) moiety and water molecules. The distance between the adjacent Cu(3)(II)W(2)(V) chains within the layer is 11.12 A along the a axis. The layers are connected by H-bonds of NCN-NDMF-NCN linkages into 3-D supramolecular architecture. The magnetic properties correspond to a dominant ferromagnetic coupling within the Cu(II)(3)W(V)(2) pentamer units (J = +35(4) cm(-1)) and much weaker effective AF interunit coupling which include both intra- and inter-3,2-chain interactions between pentamers (J' = -0.05(1) cm(-1)).     

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: synthesis,structure, and fluorescent properties of [Ln2(DNBA)4(DMF)8][Mo6O19] (DNBA = 3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo(6)O(19)(2)(-), has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo(6)O(19)] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.     

Ball-and-socket stacking of supercharged geodesic polyarenes: bonding by interstitial lithium ions

Unprecedented supramolecular stacks of highly reduced geodesic pi-systems were prepared by the reduction of the derivatized fullerenes Me(5)C(60)H and Ph(5)C(60)H and corannulene with lithium metal (R(5)C(60)(5)(-)/Cor(4)(-)/9Li(+)). The host--guest assemblies form because of the enhanced electrostatic interactions between the lithium cations and the anionic moieties, in addition to the structural compatibility between the curved hydrocarbons. The high stability of these new supramolecular assemblies (heterodimers) enables the introduction of another organization motif to the system. This is achieved by using tethered corannulenes as host molecules, which leads to the formation of tethered bis-heterodimers ((Me(5)C(60)(5)(-)/Cor(4)(-))(2)(CH(2))(8)/18Li(+)).     

Polymeric networks of copper(II) using succinate and aromatic N-N donor ligands: synthesis, crystal structure, magnetic behaviour and the effect of weak interactions on their crystal packing

Four succinato-bridged complexes of copper(II) have been synthesized. Complex 1, [Cu(2)(mu-OH(2))(2)L(bpy)(2)(NO(3))(2)](n) and 2, [Cu(2)(mu-OH(2))(2)L(phen)(2)(NO(3))(2)](n)(bpy = 2,2[prime or minute]-bipyridine; phen = 1,10-phenanthroline and LH(2)= succinic acid) exhibit 1D coordination polymer structures where both the nitrate ions are directly linked to the copper(ii) producing synthons in a 2D sheet. A novel 2D grid-like network, ([Cu(4)L(2)(bpy)(4)(H(2)O)(2)](ClO(4))(4)(H(2)O))n3, is obtained upon changing the nitrate by perchlorate anion in complex 1, where the channels are occupied by the anions. On changing the nitrate by tetrafluoroborate anion in complex 2, a novel octanuclear complex, [Cu(8)L(4)(phen)(12)](BF(4))(8).8H(2)O 4, is isolated. The coligand bpy and phen in these complexes show face-to-face (in 1,2,3,4) or edge-to-face (in 4 )pi-pi interactions forming the multidimensional supramolecular architectures. Interestingly, the appearance of edge-to-face pi-pi interactions in complex facilitates the formation of discrete octanuclear entities. Variable-temperature (300-2 K) magnetic measurements of complexes have been done. Complexes 1 and 2 show very weak antiferromagnetic (OOC-CH(2)-CH(2)-COO) and ferromagnetic coupling (mu-H(2)O). Complex 3 also shows antiferromagnetic (syn-syn mu-OCO), and ferromagnetic coupling (mu-O of the -COO group). Complex 4 with two types (syn-syn and syn-anti) of binding modes of the carboxylate group shows strong antiferromagnetic interaction.     

Diisocyanoarene-linked pentacarbonylvanadate(I-) ions as building blocks in a supramolecular charge-transfer framework assembled through noncovalent π-π and contact ion interactions

Three synthetic routes to the unusual supramolecular complex ([Cp(2)Co](2)[{(OC)(5)V}(2)(μ-1,4-CNC(6)Me(4)NC)])(∞), which was crystallographically characterized, are presented. The dianion [{(OC)(5)V}(2)(μ-1,4-CNC(6)Me(4)NC)](2-) constitutes the first subvalent organometallics featuring a diisocyanoarene linker.     

Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions

New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), [Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(iii) compounds, 2 is a mixed-valence dinuclear manganese(iii/iv) compound, and 3 is a trinuclear compound containing two manganese(iii) ions and a sodium(i) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions.     

On the road to a termolecular complex with acetone: a heterometallic supramolecular network [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]

A novel heterometallic supramolecular network [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]](2)( infinity ) has been prepared by codeposition of the volatile mono(acetone) adduct [Rh(2)(O(2)CCF(3))(4).eta(1)-OCMe(2)](2) and copper(I) trifluoroacetate, [Cu(4)(O(2)CCF(3))(4)]. The product is of interest from the viewpoints of gas-phase supramolecular synthesis and a rare bridging coordination mode of acetone. It has been fully characterized by IR and NMR spectroscopy, elemental analysis, and X-ray diffraction. An X-ray structure revealed a layered 2D arrangement of the heterometallic [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]] units built by axial intermolecular interactions of the open electrophilic Rh(II) and Cu(I) centers and O-atoms of neighboring carboxylate groups. The coordination of the acetone molecules within the [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]] unit is asymmetric with the Rh-O and Cu-O distances being 2.2173(15) and 2.7197(17) A, respectively. This work shows the potential of gas-phase deposition that may provide additional possibilities in supramolecular synthesis by utilizing intermolecular interactions and coordination bonds in a new way compared with conventional solution chemistry.     

Using a kinase/phosphatase switch to regulate a supramolecular hydrogel and forming the supramolecular hydrogel in vivo

We have designed and synthesized a new hydrogelator Nap-FFGEY (1), which forms a supramolecular hydrogel. A kinase/phosphatase switch is used to control the phosphorylation and dephosphorylation of the hydrogelator and to regulate the formation of supramolecular hydrogels. Adding a kinase to the hydrogel induces a gel-sol phase transition in the presence of adenosine triphosphates (ATP) because the tyrosine residue is converted into tyrosine phosphate by the kinase to give a more hydrophilic molecule of Nap-FFGEY-P(O)(OH)(2) (2); treating the resulting solution with a phosphatase transforms 2 back to 1 and restores the hydrogel. Electron micrographs of the hydrogels indicate that 1 self-assembles into nanofibers. Subcutaneous injection of 2 in mice shows that 80.5 +/- 1.2% of 2 turns into 1 and results in the formation of the supramolecular hydrogel of 1 in vivo. This simple biomimetic approach for regulating the states of supramolecular hydrogels promises a new way to design and construct biomaterials.     

New mode of coordination for the dinitrogen ligand: formation, bonding, and reactivity of a tantalum complex with a bridging N(2) unit that is both side-on and end-on.

The reaction of a mixture of 1 equiv of PhPH(2) and 2 equiv of PhNHSiMe(2)CH(2)Cl with 4 equiv of Bu(n)Li followed by the addition of THF generates the lithiated ligand precursor [NPN]Li(2).(THF)(2) (where [NPN] = PhP(CH(2)SiMe(2)NPh)(2)). The reaction of [NPN]Li(2).(THF)(2) with TaMe(3)Cl(2) produces [NPN]TaMe(3), which reacts under H(2) to yield the diamagnetic dinuclear Ta(IV) tetrahydride ([NPN]Ta)(2)(mu-H)(4). This hydride reacts with N(2) with the loss of H(2) to produce ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)), which was characterized both in solution and in the solid state, and contains strongly activated N(2) bound in the unprecedented side-on end-on dinuclear bonding mode. A density functional theory calculation on the model complex [(H(3)P)(H(2)N)(2)Ta(mu-H)](2)(mu-eta(1):eta(2)-N(2)) provides insight into the molecular orbital interactions involved in the side-on end-on bonding mode of dinitrogen. The reaction of ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)) with propene generates the end-on bound dinitrogen complex ([NPN]Ta(CH(2)CH(2)CH(3)))(2)(mu-eta(1):eta(1)-N(2)), and the reaction of [NPN]Li(2).(THF)(2) with NbCl(3)(DME) generates the end-on bound dinitrogen complex ([NPN]NbCl)(2)(mu-eta(1):eta(1)-N(2)). These two end-on bound dinitrogen complexes provide evidence that the bridging hydride ligands are responsible for the unusual bonding mode of dinitrogen in ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)). The dinitrogen moiety in the side-on end-on mode is amenable to functionalization; the reaction of ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)) with PhCH(2)Br results in C-N bond formation to yield [NPN]Ta(mu-eta(1):eta(2)-N(2)CH(2)Ph)(mu-H)(2)TaBr[NPN]. Nitrogen-15 NMR spectral data are provided for all the tantalum-dinitrogen complexes and derivatives described.     

Synthesis, structure and photophysical properties of two transitional metal supramolecular complexes

Two supramolecular complexes: [Co(2,6-PDC)(Hdmpz)3]·H2O (1) and [Zn(2,6-PDC)(Hdmpz)2] (2) {2,6-PDC=pyridine-2,6-dicarboxylic acid, Hdmpz=3,5-dimethylpyrazol}, self-assembles via O-H?O and N-H?O hydrogen bondings into supramolecular networks, which are characterized by elemental analyses, IR spectra and single crystal X-ray diffraction analysis. Both of them consist of two-dimensional networks that are stacked together by typical hydrogen bonding interactions (i.e. O-H?O and N-H?O), which often play important roles in the formation of low-dimensional into high-dimensional supramolecular networks. In addition, quantum chemistry calculations and surface photovoltage spectroscopy are performed firstly with the complexes.     

One-dimensional oxalato-bridged Cu(II), Co(II), and Zn(II) complexes with purine and adenine as terminal ligands

The reaction of nucleobases (adenine or purine) with a metallic salt in the presence of potassium oxalate in an aqueous solution yields one-dimensional complexes of formulas [M(mu-ox)(H(2)O)(pur)](n) (pur = purine, ox = oxalato ligand (2-); M = Cu(II) [1], Co(II) [2], and Zn(II) [3]), [Co(mu-ox)(H(2)O)(pur)(0.76)(ade)(0.24)](n)(4) and ([M(mu-ox)(H(2)O)(ade)].2(ade).(H(2)O))(n) (ade = adenine; M = Co(II) [5] and Zn(II) [6]). Their X-ray single-crystal structures, variable-temperature magnetic measurements, thermal behavior, and FT-IR spectroscopy are reported. The complexes 1-4 crystallize in the monoclinic space group P2(1)/a (No. 14) with similar crystallographic parameters. The compounds 5 and 6 are also isomorphous but crystallize in the triclinic space group P (No. 2). All compounds contain one-dimensional chains in which cis-[M(H(2)O)(L)](2+) units are bridged by bis-bidentate oxalato ligands with M(.)M intrachain distances in the range 5.23-5.57 A. In all cases, the metal atoms are six-coordinated by four oxalato oxygen atoms, one water molecule, and one nitrogen atom from a terminal nucleobase, building distorted octahedral MO(4)O(w)N surroundings. The purine ligand is bound to the metal atom through the most basic imidazole N9 atom in 1-4, whereas in 5 and 6 the minor groove site N3 of the adenine nucleobase is the donor atom. The crystal packing of compounds 5 and 6 shows the presence of uncoordinated adenine and water crystallization molecules. The cohesiveness of the supramolecular 3D structure of the compounds is achieved by means of an extensive network of noncovalent interactions (hydrogen bonds and pi-pi stacking interactions). Variable-temperature magnetic susceptibility measurements of the Cu(II) and Co(II) complexes in the range 2-300 K show the occurrence of antiferromagnetic intrachain interactions.     

Anion induced formation of supramolecular associations involving lone pair-π and anion-π interactions in Co(II) malonate complexes: experimental observations, Hirshfeld surface analyses and DFT studies

Three Co(II)-malonate complexes, namely, (C(5)H(7)N(2))(4)[Co(C(3)H(2)O(4))(2)(H(2)O)(2)](NO(3))(2) (1), (C(5)H(7)N(2))(4)[Co(C(3)H(2)O(4))(2)(H(2)O)(2)](ClO(4))(2) (2), and (C(5)H(7)N(2))(4)[Co(C(3)H(2)O(4))(2)(H(2)O)(2)](PF(6))(2) (3) [C(5)H(7)N(2) = protonated 2-aminopyridine, C(3)H(4)O(4) = malonic acid, NO(3)(-) = nitrate, ClO(4)(-) = perchlorate, PF(6)(-) = hexafluorophosphate], have been synthesized from purely aqueous media, and their crystal structures have been determined by single crystal X-ray diffraction. A thorough analysis of Hirshfeld surfaces and fingerprint plots facilitates a comparison of intermolecular interactions in 1-3, which are crucial in building supramolecular architectures. When these complexes are structurally compared with their previously reported analogous Ni(II) or Mg(II) compounds, a very interesting feature regarding the role of counteranions has emerged. This phenomenon can be best described as anion-induced formation of extended supramolecular networks of the type lone pair-π/π-π/π-anion-π/π-lone pair and lone pair-π/π-π/π-anion involving various weak forces like lone pair-π, π-π, and anion-π interactions. The strength of these π contacts has been estimated using DFT calculations (M06/6-31+G*), and the formation energy of the supramolecular networks has been also evaluated. The influence of the anion (NO(3)(-), ClO(4)(-), and PF(6)(-)) on the total interaction energy of the assembly is also studied.     

Structure, formation, and dynamics of Mo(12) and Mo(16) oxothiomolybdenum rings containing terephtalate derivatives

The influence of rigid or semirigid dicarboxylate anions, terephtalate (TerP(2-)), isophtalate (IsoP(2-)), and phenylenediacetate (PDA(2-)) on the self-condensation process of the [Mo(2)O(2)S(2)](2+) dioxothio cation has been investigated. Three new molybdenum rings, [Mo(12)O(12)S(12)(OH)(12)(TerP)](2-) ([Mo(12)TerP](2-)), [Mo(16)O(16)S(16)(OH)(16)(H(2)O)(4)(PDA)(2)](4-) ([Mo(16)(PDA)(2)](4-)), and [Mo(16)O(16)S(16)(OH)(16)(H(2)O)(2)(IsoP)(2)](4-) ([Mo(16)(IsoP)(2)](4-)) have been isolated and unambiguously characterized in the solid state by single-crystal X-ray studies and in solution by various NMR methods and especially by diffusion-correlated NMR ((1)H DOSY) spectroscopy, which was shown to be a powerful tool for the characterization and speciation of templated molybdenum ring systems in solution. Characterization by FT-IR and elemental analysis are also reported. The dynamic and thermodynamic properties of both the sixteen-membered rings were studied in aqueous medium. Specific and distinct behaviors were revealed for each system. The IsoP(2-)/[Mo(2)O(2)S(2)](2+) system gave rise to equilibrium, involving mono-templated [Mo(12)IsoP](2-) and bis-templated [Mo(16)(IsoP)(2)](4-) ions. Thermodynamic parameters have been determined and showed that the driving-force for the formation of the [Mo(16)(IsoP)(2)](4-) is entropically governed. However, whatever the conditions (temperature, proportion of reactants), the PDA(2-)/[Mo(2)O(2)S(2)](2+) system led only to a single compound, the [Mo(16)(PDA)(2)](4-) ion. The latter exhibits dynamic behavior, consistent with the gliding of both the stacked aromatic groups. Stability and dynamics of both Mo(16) rings was related to weak hydrophobic or pi-pi stacking inter-template interactions and inner hydrogen-bond network occurring within the [Mo(16)(IsoP)(2)](4-) and [Mo(16)(PDA)(2)](4-) ions.     

Strong supramolecular binding of Li(+)@C60 with sulfonated meso-tetraphenylporphyrins and long-lived photoinduced charge separation

A supramolecular binding occurred between lithium ion encapsulated [60]fullerene (Li(+)@C(60)) and sulfonated tetraphenylporphyrins ([MTPPS](4-) M = H(2) and Zn) in a benzonitrile solution. Photoexcitation of Li(+)@C(60)/[MTPPS](4-) results in formation of a long-lived charge-separated state by photoinduced electron transfer.     

Combining coordination and supramolecular chemistry for the formation of uranyl-organic hybrid materials

Three hybrid compounds have been synthesized through hydrothermal reactions of UO(2)(NO(3))(2)·6H(2)O with 4-halobenzoic acid (X = Cl, Br, I). The formation of these compounds utilizes a composite synthesis methodology that explicitly employs aspects of both coordination chemistry and supramolecular chemistry (namely halogen···halogen interactions).     

Self-assembly of D-penicillaminato M6M'8 (M = Ni(II), Pd(II), Pt(II); M' = Cu(I), Ag(I)) clusters and their organization into extended La(III)M6M'8 supramolecular structures

A series of chiral M(6)M'(8) cluster compounds having twelve free carboxylate groups, [M(6)M'(8)(D-pen-N,S)(12)X](5-) (M/M'/X = Pd(II)/Ag(I)/Cl(-) ([1](5-)), Pd(II)/Ag(I)/Br(-) ([2](5-)), Pd(II)/Ag(I)/I(-) ([3](5-)), Ni(II)/Ag(I)/Cl(-) ([4](5-)), Pt(II)/Ag(I)/Cl(-) ([5](5-)), Pd(II)/Cu(I)/Cl(-) ([6](5-)); D-H(2)pen = D-penicillamine), in which six cis-[M(D-pen-N,S)(2)](2-) square-planar units are bound to a [M'(8)X](7+) cubic core through sulfur-bridges, was synthesized by the reactions of cis-[M(D-pen-N,S)(2)](2-) with M' in water in the presence of halide ions. These M(6)M'(8) clusters readily reacted with La(3+) in aqueous buffer to form La(III)(2)M(6)M'(8) heterotrimetallic compounds, La(2)[1](CH(3)COO), La(2)[2](CH(3)COO), La(2)[3](CH(3)COO), La(2)[4](CH(3)COO), La(2)[5](CH(3)COO) and La(2)[6]Cl, in which the M(6)M'(8) cluster units are linked by La(3+) ions through carboxylate groups in a 1?:?2 ratio. While the La(III)(2)M(6)Ag(I)(8) compounds derived from [1](5-), [2](5-), [3](5-), [4](5-) and [5](5-) have a 1D helix supramolecular structure with a right-handedness, the La(III)(2)Pd(II)(6)Cu(I)(8) compound derived from [6](5-) has a 2D sheet-like structure with a triangular grid of the Pd(II)(6)Cu(I)(8) cluster units. When aqueous HCl was added to the reaction solution of [6](5-) and La(3+), another La(III)(2)Pd(II)(6)Cu(I)(8) heterotrimetallic compound, La(2)[6]Cl·HCl, in which the Pd(II)(6)Cu(I)(8) cluster units are linked by La(3+) ions to form a 2D structure with a rectangular grid, was produced. The solid-state structures of these La(III)(2)M(6)M'(8) compounds, determined by single-crystal X-ray crystallography, along with the spectroscopic properties of the M(6)M'(8) cluster compounds in solution, are described.