Extended Hydrogen-Bonded Molybdenum Arrays Derived from Carboxylic Acids and Dianilines: ROP Capability of the Complexes and Parent Acids and Dianilines

From reactions involving sodium molybdate and dianilines [2,2′ -(NH2 )C6H4 ]2 (CH2 )n (n = 0, 1, 2) and amino-functionalized carboxylic acids 1,2-(NH2 )(CO2H)C6H4 or 2-H2NC6H3 -1,4-(CO2H)2 , in the presence of Et3N and Me3SiCl, products adopting H-bonded networks have been characterized. In particular, the reaction of 2,2′ -diaminobiphenyl, [2,2′ -NH2 (C6H4 )]2 , and 2-aminoterephthalic acid, H2NC6H3 -1,4-(CO2H)2 , led to the isolation of [(MoCl3 [2,2′ -N(C6H4 )]2 }{HNC6H3 -1-(CO2 ),4- (CO2H)]\ub72[2,2′ -NH2 (C6H4 )]2 \ub73.5MeCN (1\ub73.5MeCN), which contains intra-molecular N–H\ub7\ub7\ub7Cl Hbonds and slipped π\ub7\ub7\ub7π interactions. Similar use of 2,2′ -methylenedianiline, [2,2′ -(NH2 )C6H4 ]2CH2 , in combination with 2-aminoterephthalic acid led to the isolation of [MoCl2 (O2CC6H3NHCO2SiMe3 ) (NC6H4CH2C6H4NH2 )]\ub73MeCN(2\ub73MeCN). Complex 2 contains extensive H-bonds between pairs of centrosymmetrically-related molecules. In the case of 2,2′ ethylenedianiline, [2,2′ -(NH2 )C6H4 ]2CH2CH2 , and anthranilic acid, 1,2-(NH2 )(CO2H)C6H4 , reaction with Na2MoO4 in the presence of Et3N and Me3SiCl in refluxing 1,2-dimethoxyethane afforded the complex [MoCl3 {1,2-(NH)(CO2 )C6H4 }{NC6H4 CH2CH2C6H4NH3 }]\ub7MeCN (3\ub7MeCN). In 3, there are intra-molecular bifurcated H-bonds between NH3 H atoms and chlorides, whilst pairs of molecules H-bond further via the NH3 groups to the non-coordinated carboxylate oxygen, resulting in H-bonded chains. Complexes 1 to 3 have been screened for the ring opening polymerization (ROP) of both ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) using solvent-free conditions under N2 and air. The products were of moderate to high molecular weight, with wide 0 values, and comprised several types of polymer families, including OH-terminated, OBn-terminated (for PCL only), and cyclic polymers. The results of metal-free ROP using the dianilines [2,2′ -(NH2 )C6H4 ]2 (CH2 )n (n = 0, 1, 2) and the amino-functionalized carboxylic acids 1,2-(NH2 )(CO2H)C6H4 or 2-H2NC6H3 -1,4-(CO2H)2 under similar conditions (no BnOH) are also reported. The dianilines were found to be capable of the ROP of δ-VL (but not ε-CL), whilst anthranilic acid outperformed 2-aminoterephthalic acid for both ε-Cl and δ-VL

Effect of Alkyl Chain Length and Linker Atom on the Crystal Packing in 6,12-Dialkoxy- And 6,12-Dialkylsulfanyl-Benzo[1,2- b:4,5- b′]bis[ b]benzothiophenes

The effect of varying the chain length on the solid state conformation and packing of 6,12-dialkoxy- and 6,12-dialkylsulfanyl-benzo[1,2-b:4,5-b′]bis[b]benzothiophenes has been studied. The compounds were prepared by SNAr reaction of 6,12-difluorbenzo[1,2-b:4,5-b′]bis[b]benzothiophene with alkoxides or alkanethiolates derived from C7-C10 alcohols and alkanethiols. Single crystal X-ray diffraction analysis revealed that all but two compounds crystallize in the triclinic space group P1. Two compounds were obtained as monoclinic crystals with space group P21/c. The alkoxy substituted compounds adopted a molecular conformation with a step from the core and a gauche conformation about the C1′-C2′ bond placing the alkyl chains close to parallel with the pentacyclic arene ring system, whereas in the alkylsufanyl derivatives, the alkyl chains were arranged strongly deviated from the plane of the ring, with the sulfur atom antiperiplanar to C3′ of the alkyl chain. NMR measurement of T1 relaxation in CDCl3 showed both the alkoxy and alkylsulfanyl substituents to be freely rotating at ambient temperature in solution, indicating the orientation of the chains in the solid state was due to packing interactions during crystallization