From Nongelating to Gelating: Synthesis and Structural Self‐Assembling Property Relationships of a Homologous Series of Oligo(amide–triazole)s

A homologous series of oligo(amide–triazole)s (OAT) [ OAT‐CO₂H‐2 n and OAT‐COPrg‐(2 n +1) ] with an increasing number of primary amide (CONH) and triazole hydrogen‐bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self‐assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen‐bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non‐organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the T_gel value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole C? H groups were involved in the hydrogen‐bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths ( OAT‐CO₂H‐6 and OAT‐CO₂H‐12 ) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen‐bonding units exhibited self‐sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state.     

An unprecedented 8-fold interpenetrating diamondoid-like coordination polymer containing a Cu+(4)(RCO2)(4) cluster as connecting node

The reaction of Cu(I)(CH(3)CN)(4)BF(4) with 4-pyridylacrylic acid (4-HPYA) affords an unprecedented 8-fold interpenetrating diamondoid-like coordination polymer network [Cu(I)(3)(4-PYA)(2)(H(2)O)(BF(4)) ] (1) with a Cu(+)(4)(CO(2))(4) cluster as connecting node. The interpenetration in metal coordination polymers is the highest degree ever found within diamondoid nets containing a cluster as connecting note. Its fluorescent property was also reported.     

N‐(Ferrocenecarbonyl)‐N′‐(quinolin‐8‐yl)thio­urea

In the title compound, [Fe(C₅H₅)(C₁₆H₁₂N₃OS)], the 8‐am­inoquinoline and acyl­thio­urea moieties are almost planar. There are two perpendicular arrangements of the mol­ecules in the crystal with slightly different conformations. The two cyclo­penta­dienyl rings in each mol­ecule are parallel and eclipsed.     

Bis[1,1′‐bis(diphenylphosphino)ferrocenium] hexadecachlorotetraantimony(III) ethanol solvate

In the title compound, [Fe(C₁₇H₁₄P)₂]₂[Sb₄Cl₁₆]·C₂H₆O, the Fe atoms lie on inversion centres and the pairs of cyclopentadienyl rings are consequently in a fully staggered conformation. The centrosymmetric anionic clusters formed by [Sb₄Cl₁₆]^4? are surrounded by the cations and are held together by weak C—H?Cl interactions. These formations stack along the a axis to form columns, and the columns are interconnected by another weak C—H?Cl interaction along the b axis.     

Photoinduced [4 + 4] cycloadditions of o-quinones with oxazoles

[reaction: see text] Photocycloadditions of 9,10-phenanthraquinone (PQ) with oxazoles (1a and 1b) gave [4 + 4] products 2 with the O=C-C=O functionality in PQ and the 2-azadiene moiety in oxazole as 4pi addends. Photoreactions of 1-acetylisatin (IS) with 1a, 1c, and 1d gave [4 + 4] product A, which underwent further [2 + 2] reactions with another (3)IS to furnish 5. These regioselective and diastereoselective [4 + 4] photocycloadditions are rationalized by the intervening of the key conformers for ISC and bond formation of the most stable 1,6-diradical intermediates.     

Synthesis and Characterization of 1,8-bis(ferrocenylmethyl)-5,5,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, a Macrocyclic Ligand and its Complexes

A new diferrocenyl-substituted macrocyclic ligand (H₂L) and its complexes ML(M = Cu^II, Ni^II, Zn^II, Cd^II) were prepared and characterized by IR, elemental analysis, absorption spectra and FAB mass spectra. The ferrocenyl-substituted macrocyclic ligand was characterized by single crystal X-ray diffraction analysis. The superconjugative effect of the cyclopentadienyl (CP) rings increase the activity of the hydrogen atoms in the tetra-azacyclotetradecane macrocyclic ligand. The imine nitrogen atoms lose two protons and coordinate to the metal. The electrochemical properties of these compounds are discussed.     

9,10‐Di­phenyl‐9,10‐epi­dioxy­anthra­cene and 9,10‐di­hydro‐10,10‐di­methoxy‐9‐phenyl­anthracen‐9‐ol

9,10‐Di­phenyl‐9,10‐epi­dioxy­anthracene, C₂₆H₁₈O₂, (I), was accidentally used in a photo­oxy­genation reaction that produced 9,10‐di­hydro‐10,10‐di­methoxy‐9‐phenyl­anthracen‐9‐ol, C₂₂H₂₀O₃, (II). In both compounds, the phenyl rings are approximately orthogonal to the anthracene moiety. The conformation of the anthracene moiety differs as a result of substitution. Intramolecular C—H⃛O interactions in (I) form two approximately planar S(5) rings in each of the two crystallographically independent mol­ecules. The packing of (I) and (II) consists of molecular dimers stabilized by C—H⃛O interactions and of molecular chains stabilized by O—H⃛O interactions, respectively.