Construction Of Multifunctional Supramolecular Organometallic Macrocycles Via Coordination-Driven Self-assembly (Pt-N)

Supramolecular chemistry is one of the frontier research areas in molecular sciences. In the history of supromolecular chemistry study, metallacycles have play an important role. Recently, construction of self-assembled metallasupramolecular structures based on coordination-driven self-assembly has attracted considerable attention because of their potential applications in host-guest chemistry, catalysis, materials science, nanomedicine. This thesis focuses on the synthesis, structure and preliminary photoelectric properties of novel organometallic macrocycles. Mainly in the following aspects:1. A new family of60°dendritic di-Pt(II) acceptor tectons have been successfully designed and synthesized, from which a series of novel triangular metallodendri-mers were prepared via [3+3] coordination-driven self-assembly. The structures of newly designed triangular metallodendrimers are characterized by multinuclear NMR (1H and31P),1H DOSY NMR, mass spectrometry (CSI-TOF-MS), and elemental analysis. The shape and size of all supramolecular dendritic triangles were investigated with PM6semi-empirical molecular orbital methods.2. The design and self-assembly of multifunctional rhomboidal metallodendri-mers via coordination-driven self-assembly are studied systematically. By employing newly designed60°ditopic donor linkers substituted with Frechet-type dendrons and functional120°rigid di-Pt(Ⅱ) acceptor subunits, a variety of [G-1]-[G-3] rhomboidal metallodendrimers with well-defined shape and size were prepared in high yields. The supramolecular metallodendrimers were characterized with multinuclear NMR (1H and31P), mass spectrometry (CSI-TOF-MS), and elemental analysis. The shape and size of all rhomboidal metallodendrimers were investigated with semi-empirical molecular orbital method. Besides, by means of electrochemistry analysis of rhomboidal organometallic macrocycles containing ferrocene functional groups electrochemical properties were studied.3. Based on the previous research work as well as the compound of pyrene unique fluorescent properties, A new family of120°di-Pt(Ⅱ) acceptor tectons containing pyrene functional groups have been successfully designed and synthesized, from which a series of novel "two-component" rhomboidal organometallic macrocycles were prepared via [2+2] coordination-driven self-assembly. Further-more, we studied these large metal ring optical properties.4. A series of new platinum bisferrocenylacetylide complexes have been synthesized utilizing the coupling reaction of trans-Pt complexes with C-H bonds in alkynes as key steps. These new bimetallic dendrimers were fully characterized by multinuclear NMR (1H,13C, and31P) and mass spectrometry (MALD1-TOF-MS and CSI-TOF-MS). Electrochemical studies of these complexes were carried out and revealed that all of the redox moieties are stable, independent, and electrochemically active. In addition, all metallodendrimers show one-electron reaction responses, and the increased sizes of these complexes did not exhibit a dramatic influence on the diffusion coefficient.5. Based on tetrathiafulvalene derivatives in fullerene recognition application, A bivalent, tweezer-like design in which two units of the recognizing fragment are connected covalently by means of an adequate spacer has been designed and synthesized, from which a series of well-defined shape and size organometallic macrocycles were prepared via coordination-driven self-assembly. Meanwhile, functional organometallic macrocycles in fullerene recognition application has done a preliminary study.