Hydrogen Bond Assembling Molecular Gyroscopes

Crystalline molecular gyroscopes, as a kind of amphidynamic crystals which is suggested by the presence of a rigid ordered component and a highly mobile component, is a novel material form. In the last few years, they had aroused the interesting of materials scientist and chemist, due to their potentially characteristic properties in photic, electronic, magnetic, and acoustic domians.Currently, the main problems about molecular gyroscope study require to be solved as below:(1) in crystalline state, solvent molecules entered the interal of gyroscopes acting as spacers. (2) Single molecule with neighboring molecules in crystals showed interlocking forms-arranged mutual impedes the rotation of the rotor. (3) Using olefin metathesis to close the aliphatic chains as ribs between two stators in the protection of the rotor tends to make olefin metathesis occur at the same sides, but it's will very complication to avoid the situation by distributing the reaction steps. We herein have synthesized a class of supramolecular structure consisting of molecular gyroscopes assembled by hydrogen bond array, and researched on their properties initially. Meanwhile, we have found some interesting result about organic synthesis and carried some methodologies research.This dissertation mainly contains four parts:(1) Design and synthesis of 2-ureido-4[1H]-pyrimidinone as quadruply hydrogen bond array assembling molecular gyroscopes. (2) Urea-based assembly of molecular gyroscopes. (3) A facile preparation for substituted 9-aryl-9H-fluorenes from triarylcarbinols. (4) Novel blue organic light emitting materials base on anthracene derivatives.1. Design and synthesis of 2-ureido-4[1H]-pyrimidinone as quadruply hydrogen bond array assembling molecular gyroscopes.Utilizing molecular gyroscope with a bis-triphenylmethyl stator and a phenylene rotator framework, we had designed and synthesized twelve 2-ureido-4[1H]-pyrimidinone as quadruply hydrogen bond array assembling molecular gyroscopes by employed multiple amine gyroscopes precursor recting with CDI-activated amino-pyrimidinones.(1) Initially, we synthesized some methyl-pyrimidinone assembling molecular gyroscope (2-13b, e, i), and found they were difficult to dissolve even in DMSO. The 1H NMR showed that only a broad peak at 12.8 ppm without assembling ureido-proton signal peaks, which indicated that the assemblied hydrogen bond had been completely destroyed in DMSO. In order to improve solubility, we introducted n-heptanyl, n-tridecanyl, and iso-heptanyl aliphatic chains to 2-ureido-4[1H]-pyrimidinone, attempting to improve their solubility, but found it's invalid.(2) Furthermore, employed the high dilution technique in connecting 2-ureido-4[1H]-pyrimidinones to molecular gyroscope precursors, we prepared some diffluent terminal materials which were still diffcult to dissolve after washing with methanol. The 1H NMR showed that these molecular gyroscopes synthesized by high dilution technique exhibited obvious hydrogen bond assembling behavior in chloroform. For example, In the 1H NMR spectrum of 2-13k in CDCl3 the NH proton signals are found at 13.14,11.89, and 10.20 ppm, indicative of extensive hydrogen bonding. Unfortunatly, we haven't got the crystal about this kind compounds after attempting various crystal grownth methods, and the dynamics research about the rotor has needed to be further 13C CPMAS-DD determined.2. Ureido-group assembling molecular gyroscopes.In addition, we have synthesized twelve ureido-group assembling molecular gyroscopes by employing three isocyanates reacting with primary amine on the molecular gyroscope precusors which have different aliphatic chains. This class of compounds is gelationous in apolar and weak porlar solvents such as CDCl3, but is diffluent after adding a little polar solvent such as mathenol to destroy assembling hydrogen bond, exhibiting obvious supramolecular gel property. In the 1H NMR spectrum in CDCl3 the NH proton signals are found obviously, but nothing in CDCl3/methanol mixture solvent, indicative of moderate hydrogen bonding. The dynamics research about the rotor and gelatinous property have needed to be further determined.3. A facile preparation for substituted 9-aryl-9H-fluorenes from triarylcarbinols.We have found a facile method for synthesis of substituted 9-aryl-fluorenes from of triarylcarbinols in the presence of TsOH in a benzene (or CH2Cl2) in moderate yield, and found that the structures of different 9-aryl fluorenes as EAS reaction products were determined by the substituted groups on the aryl ring of triarylcarbinols. Just as the binaphthalene, compound 4-2g has the similar racemization of axial chirality which was estimated by variable-temperature 1H NMR. Their electronic properties were investigated by UV/Vis absorption spectra. Further attempt to prepare OFET (Organic Field Effect Transistor) with the substituted 9-aryl-fluorenes as initial materials is under way.4. Novel blue organic light emitting materials base on anthracene derivatives.A series of blue emitters containing anthracenyl group were synthesized in moderate yields by Sonogashira cross-coupling reaction and characterized by general optical methods. From our preliminary investigation of these compounds, all of them show high melting points and decomposition temperature. Moreover, luminescence properties clearly indicated that these new anthracene-based conjugated compounds are highly promising materials for the development of stable, blue color, electroluminescent compounds. Further investigation on thermal behavior and electroluminescent properties of these new molecules is in progress.