Synthesis And Solid-state Polymerization Of Diacetylene Derivatives Containing Ferrocencyl

Nonlinear optics(NLO), as a new subject, has showed great application foreground in the fields of information communication, data storage, optical information processing, etc. It can solve some "bottlenecks" brought out by microelectronics technology, so the research on the new NLO materials with larger third-order nonlinear coefficient and ultrafast response attracted great attention. Polydiacetylene (PDA) derivatives as an organic polymer NLO has the advantages of large nonlinear coefficient, fast response time, chemical and thermal stability, excellent performance of the molecular design, which may meet the requirement of the future optical devices.The PDA, being a one-dimensionalπ-conjugated system which shows NLO properties as well as electronic and photonics properties due to itsπ-conjugated systems. DAs exhibit topochemical solid-state polymerization and are capable of forming liquid crystals and films as well as single crystal. Polymerization of Diacetylenes(DA) can be initiated by heat, UV or y irradiation to form PDA.In view of the effect of the substituted side chains of diacetylene monomers on topochemical solid-state polymerization, phenyl ferrocene structure in two different locations were introduced into diacetylene for meeting the requirements of topochemical polymerization and increasing the effectiveπ-conjugated length.1. Two series of diacetylene derivatives containing ferrocencyl were synthesized (Schemel) and characterized by 1H Nuclear Magnetic Resonance spectra ('HNMR), 13C Nuclear Magnetic Resonance spectra (13CNMR), Mass spectra (MS) and Infra-red spectra (IR). 2. The single crystals of compounds 4a and 3b which are both new compounds not reported before were also cultivated in this article.3. The UV absorption spectra of two series of the monomer (a, b) in solution were showed that the absorption increased with increasing degree of molecular conjugation and had peak red shift.4. The topochemical solid-state polymerization properties of compound 4a and 4b were investigated in cast film, spin coating respectively. Under UV 250 nm irradiation, there are no changes in UV spectra due to low transmission of 250nm light in sample or molecular arrangement. In the case of 4a cast film had mainly molecular aggregation when being heated to 80℃, but in the case of 4b, there is a wide flat peak in the range from 500 to 700nm, indicating that polymerization occurred. To 120℃, the UV absorption of triple bond of 4a and 4b were decreased and finally disappeared, while there is a wide flat peak in the range in the long wavelength direction, indicating that polymerization occurred, but the monomer proceeded polymerization not noly in regular 1,2-addtion and 1,4-addtion but other complicated polymerization at the same time.