Orientational control of guest molecules in an organic intercalation system by host polymer tacticity

Four kinds of stereoregular poly(muconic acid)s, which are synthesized by topochemical polymerization and subsequent solid-state hydrolysis, are used as the organic host materials for intercalation. We describe the reaction behavior and layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as IR and Raman spectroscopies. We have found that the orientation of the guest molecules is controlled by the host polymer tacticity, depending on the structure of the two-dimensional hydrogen-bonding network formed in the polymer sheets of the crystals.     

Chirality transfer from guest chiral metal complexes to inorganic framework: the role of hydrogen bonding

The structure elucidation of a new zinc phosphate [Co(II)(en)(3)][Zn(4)(H(2)PO(4))(3)(HPO(4))(2)(PO(4))(2 H(2)O)(2)] (1) reveals that the racemic cobalt complex templates the zinc phosphate framework in such a way that the local C(2) point symmetry of the structural motif of the inorganic framework conforms with that of the cobalt complex pairing with it, in essence transferring its chirality to the inorganic host. An analysis of hydrogen bonding between the guest molecules and the inorganic host framework reveals that hydrogen bonding is responsible for the stereospecific structural arrangement. Upon examining previously reported chiral metal-complex-templated structures of metal phosphates, it is revealed that such hydrogen bonding is the common origin for inducing chirality transfer in metal-phosphate frameworks templated with chiral metal complexes. Crystal data of 1: orthorhombic, Pbcn (no. 60), a=10.4787(8) A, b=20.0091(14) A, c=14.9594(10) A, and Z=2.     

Structural and magnetic resolution of a two-step full spin-crossover transition in a dinuclear iron(II) pyridyl-bridged compound

A dinuclear iron(II) complex containing the new pyridyl bridging ligand, 2,5-di(2',2'-dipyridylamino)pyridine (ddpp) has been synthesised and characterised by single-crystal X-ray diffraction, magnetic susceptibility and M?ssbauer spectral methods. This compound, [Fe(2)(ddpp)(2)(NCS)(4)]4 CH(2)Cl(2), undergoes a two-step full spin crossover. Structural analysis at each of the three plateau temperatures has revealed a dinuclear molecule with spin states HS-HS, HS-LS and LS-LS (HS: high spin, LS: low spin) for the two iron(II) centres. This is the first time that resolution of the metal centres in a HS-LS ordered state has been achieved in a two-step dinuclear iron(II) spin-crossover compound. Thermogravimetric data show that the dichloromethane solvate molecules can be removed in two distinct steps at 120 degrees C and 200 degrees C. The partially de-solvated clathrate, [Fe(2)(ddpp)(2)(NCS)(4)]CH(2)Cl(2), undergoes a one-step transition with an increased transition temperature with respect to the as synthesised material. Structural characterisation of this material reveals subtle changes to the coordination geometries at each of the iron(II) centres and striking changes to the local environment of the dinuclear complex. The fully de-solvated material remains high spin over all temperatures. Interestingly, the solvent can be re-introduced into the monosolvated solid to achieve complete conversion back to the original two-step crossover material, [Fe(2)(ddpp)(2)(NCS)(4)]4 CH(2)Cl(2).     

"Pocket dendrimers" as nanoscale receptors for bimolecular guest accommodation

A new series of dendrimer receptors was prepared by combining a (tetraphenylporphinato)zinc(II) core and benzyl ether type dendritic substituents. Since one direction of the (tetraphenylporphinato)zinc(II) was not substituted by a dendritic residue, the resulting unsymmetrical dendrimers have "pockets" available for access of external substrates. Molecular modeling, NMR measurements, and zinc-coordination experiments revealed that the third-generation dendrimer of this type exhibited characteristic inclusion of coordinative pyridine guests. When diamidopyridine moiety was introduced into the dendrimer pocket, a thymine derivative was bound through complementary hydrogen bonding. Two different kinds of substrates, pyridine and thymine derivatives, were simultaneously accommodated in the nanoscale pocket and bimolecular guest accommodation was realized with the designed dendrimer receptor.     

Highly selective recognition of adenine nucleobases by synthetic hosts with a linked five-six-five-membered triheteroaromatic structure and the application to potentiometric sensing of the adenine nucleotide

A new structure for an adenine-selective host molecule, featuring the pertinent link of five-six-five-membered heteroaromatic rings and two carbamoyl NH sites, was developed. This structure provides a correctly oriented array of complementary hydrogen bonding sites for the adenine nucleobase, which exploits both Watson-Crick and Hoogsteen-type interactions. The complexation with adenine nucleobases by multiple hydrogen bonding was supported by (1)H NMR spectroscopy. This type of host displayed high selectivity in complexation, with an accompanying fluorescent response to lipophilized adenosine in CHCl(3). Furthermore, a remarkably selective potentiometric response was attained for adenosine 5'-monophosphate over 5'-GMP, 5'-CMP, and 5'-UMP by using an ion-selective electrode with a PVC-supported solvent polymeric membrane. This indicates recognition of water-soluble nucleotide guests through the membrane-water interface. These findings are expected to form a reliable basis for the development of artificial sensing systems for mononucleotides in biological systems.     

Pseudopolymorphism of aliphatic amine/4-tert-butylcalix[4]arene inclusion compounds: supramolecular stabilization as a route to polar clusters and layers

4-tert-Butylcalix[4]arene (4tBC4A) is a versatile host capable of forming a variety of 1:1 and 2:1 inclusion compounds typically stabilized through van der Waals interactions. Preliminary studies in our group have demonstrated that inclusion of n-butylamine in 4tBC4A results in a series of pseudopolymorphic inclusion compounds, including a new 3:1 inclusion motif. Using a combination of SCXRD, TGA, solid state NMR, and PXRD, we now elaborate upon the relationship between these pseudopolymorphs. We also demonstrate that larger amines demonstrate a similar degree of pseudopolymorphism, allowing for the production of customized materials using self-assembly guided by competing weak forces. Finally, we comment on the structural implications of the relative dominance such forces in the formation of calixarene-based supramolecular frameworks.     

Guest-induced supramolecular isomerism in inclusion complexes of T-shaped host 4,4-bis(4'-hydroxyphenyl)cyclohexanone

The T-shaped host molecule 4,4-bis(4'-hydroxyphenyl)cyclohexanone (1) has an equatorial phenol group and a cyclohexanone group along the arms and an axial phenol ring as the stem. The equatorial phenyl ring adopts a "shut" or "open" conformation, like a windowpane, depending on the size of the guest (phenol or o/m-cresol), for the rectangular voids of the hydrogen-bonded ladder host framework. The adaptable cavity of host 1 expands to 11x15-18 A through the inclusion of water with the larger cresol and halophenol guests (o-cresol, m-cresol, o-chlorophenol, and m-bromophenol) compared with a size of 10x13 A for phenol and aniline inclusion. The ladder host framework of 1 is chiral (P2(1)) with phenol, whereas the inclusion of isosteric o- and m-fluorophenol results in a novel polar brick-wall assembly (7x11 A voids) as a result of auxiliary C-H...F interactions. The conformational flexibility of strong O-H...O hydrogen-bonding groups (host 1, phenol guest), the role of guest size (phenol versus cresol), and weak but specific intermolecular interactions (herringbone T-motif, C-H...F interactions) drive the crystallization of T-host 1 towards 1D ladder and 2D brick-wall structures, that is, supramolecular isomerism. Host 1 exhibits selectivity for the inclusion of aniline in preference to phenol as confirmed by X-ray diffraction, 1H NMR spectroscopy, and thermogravimetry-infrared (TG-IR) analysis. The T(onset) value (140 degrees C) of aniline in the TGA is higher than those of phenol and the higher-boiling cresol guests (T(onset)=90-110 degrees C) because the former structure has more O-H...N/N-H...O hydrogen bonds than the clathrate of 1 with phenol which has O-H...O hydrogen bonds. Guest-binding selectivity for same-sized phenol/aniline molecules as a result of differences in hydrogen-bonding motifs is a notable property of host 1. Host-guest clathrates of 1 provide an example of spontaneous chirality evolution during crystallization and a two-in-one host-guest crystal (phenol and aniline), and show how weak C-H...F interactions (o- and m-fluorophenol) can change the molecular arrangement in strongly hydrogen-bonded crystal structures.     

Highly selective recognition of diols by a self-regulating fine-tunable methylazacalix[4]pyridine cavity: guest-dependent formation of molecular-sandwich and molecular-capsule complexes in solution and the solid state

The molecular recognition of methylazacalix[4]pyridine (MACP-4; 1) towards various diols was investigated by using (1)H NMR spectroscopic and X-ray diffraction analysis. As a unique macrocyclic host molecule that undergoes conformational inversions very rapidly in solution, MACP-4 has been shown to self-regulate its conformation, through the formation of different conjugations of the four bridging nitrogen atoms with their adjacent pyridine rings, to form a cavity that best fits the guest species through intermolecular hydrogen-bond, C-H...pi, and pi-pi interactions between the host and guest. As a consequence, depending upon the diol structure and geometry, MACP-4 forms a 1:1 molecular sandwich, 2:1 molecular capsule, and 1:2 butterfly-layered complex with the guests. As a result of favorable enthalpy and entropy effects, MACP-4 exhibits excellent selectivity in the recognition of resorcinol, thus resulting in a very stable 1:1 sandwich complex with resorcinol with a binding constant of 6000 (M-1). The dynamic (1)H NMR spectroscopic study demonstrated that the 1,3-alternate conformation of the macrocyclic ring of the MACP-4resorcinol complex (13) is stable at low temperature (T<243 K), and its conformational inversion requires a larger activation energy (DeltaG++=(45.5+/-2.2) kJ mol(-1)). In the presence of an excess amount of resorcinol, however, the conformational inversion of the MACP-4resorcinol complex proceeds more readily with a decreased activation energy (DeltaG++=(33.5+/-1.5) kJ mol(-1)) owing most probably to the favorable enthalpy effect of the [3...1...3]++transition state.     

Strong binding affinity of a zinc-porphyrin-based receptor for halides through the cooperative effects of quadruple C-H hydrogen bonds and axial ligation

A new type of host compound (1), tetraphenyl zinc-porphyrin (ZnTPP) that contains four triazole groups at the ortho-position of each phenyl group, has been synthesized and characterized by using (1)H, (13)C NMR, and MALDI-TOF-MS analyses. The host-guest complex formation between 1 and halides was investigated by using (1)H NMR spectroscopy in [D(6)]DMSO. The triazole, benzyl, and phenylene proton signals were shifted upfield by the addition of halides in the form of tetrabutylammonium salts, which implies that the triazole protons in 1 are allocated very closely to the porphyrin ring and are directed toward the binding pocket over the porphyrin ring during the formation of hydrogen bonds. The UV/Vis absorption spectra showed that both the Soret and Q band absorptions of 1 underwent a strong redshift due to the addition of halides. Compound 1 exhibited surprisingly strong binding affinities for the halides, where the association constants for Cl(-), Br(-), and I(-) binding were estimated to be larger than 10(8), 1.79×10(7), and 1.84×10(5) M(-1), respectively. The UV/Vis absorption changes and the result of competitive titration using 4-tert-butylpyridine indicated that the cooperative effects of axial coordination and C-H···X hydrogen bond interactions resulted in the strong binding affinity of 1 to halides.     

Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex: syntheses, structural variation, and magnetic exchange coupling pathways

The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with [M(CN)(8)](4-) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: [[Cu(3)(L)(OH(2))](2)[Mo(CN)(8)]](NO(3))(8)15 H(2)O with a structural motif that involves isolated spherical [[Cu(3)(L)(OH(2))](2)[M(CN)(8)]](8+) ions and a "string-of-pearls" type of structure [[[Cu(3)(L)](2)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with [M(CN)(8)](4-) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the [Cu(3)(L)](6+) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.     

Selective guest encapsulation by a cobalt-assembled cage molecule

Metal-assembled resorcinarene-based cages enclose space and entrap organic molecules from water. Addition of cobalt(II) ions to a neutral, aqueous solution of a resorcinarene that has iminodiacetic acids attached to its upper rim results in the formation of cages. These cages not only entrap organic molecules, but they do so in a selective manner. Guests with optimum size, shape, and polarity are preferentially entrapped. For example, selection of p-xylene is twenty thousand times more favorable than that of m-xylene. The enthalpy of resorcinarene deprotonation and cage formation was calculated by performing calorimetry studies and ranged from -305 to -348 kJ mol(-1). The change in enthalpy of guest encapsulation varied by as much as 43 kJ mol(-1). The differences in change in free energy of guest encapsulation varied by -16 kJ mol(-1). The changes in enthalpy and free energy of guest encapsulation were used to calculate the changes in entropy, which ranged from -97 to +37 J mol(-1) K(-1). An enthalpy-entropy compensation of guest encapsulation was observed.