redox systems under nano-space control, 2006, p.302

[...]... mode is described in this chapter The qd moiety also serves as a redox- active π-conjugated bridging spacer for the construction of redox- active conjugated complexes Incorporated metals play an important role as a metallic dopant to form a multiredox and multimetallic system Conjugated complexes provide redox- switching systems based on redox properties of the qd spacer Abbreviations bpy CD Cp DABCO DMF... the appearance of new redox couples (E1/ 2 = −0.19 and 0.01 V) The redox couple at −0.19 V is considered to be attributable to the vanadium-bound reduced qd moiety The plausible redox processes are shown in Scheme 1.7 1.3 Redox- Switching Properties of Conjugated Complexes with 1,4-Benzoquinonediimines Bimetallic complexes composed of π-conjugated bridging spacers and terminal redox- active transition... materials with focus on the electronic communication through a π-conjugated spacer [19] However, redox- switching systems for such transition metals have been investigated in only a few cases [20] The introduction of terminal redox- active ferrocenyl units into a 1,4-phenylenediamine (pd) bridging spacer provides a novel redox- switching system for electronic communication through the π-conjugated bridging spacer... contrast to the redox behavior of L4 in ox dichloromethane, in which the redox of the qd moiety and ferrocenyl ones is observed as an irreversible reduction wave at −1.66 V and simultaneous one-electron redox wave at 0.005 V, respectively In the case of the oxidized form L4 , electronic communication between the terminal ferrocenyl moieties ox is suppressed These results indicate that a redox switching... photophysically to provide electronic and photoactive devices [19a, 25], only a few cases have focused on redox- active bridging spacers [26] In combination with a redoxactive pd function, such complexes afford a novel redox- active donor–acceptor system The dinuclear ruthenium(II) complex 14 exhibits a redox- switchable photoinduced electron-transfer system as observed in the ruthenium complex 13 (Scheme... POT undergo complexation with VCl3 together with redox reaction, affording the conjugated complexes 10 and 11, respectively The complexation proceeds via reduction of the qd moiety with oxidation of V(III) to V(IV), in which the vanadium species is considered to play an important role in both complexation and reduction processes (Scheme 1.6) [18] The cyclic voltammogram of L1 exhibits only one redox. .. 2547 cyyeh@dragon.nchu.edu.tw Part I Redox Systems via d,π-Conjugation Chapter 1 Conjugated Complexes with Quinonediimine Derivatives Toshiyuki Moriuchi · Toshikazu Hirao Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565-0871, Japan Summary An architecturally controlled formation of conjugated complexes with redoxactive π-conjugated quinonediimine... (sq) and phenylenediamide dianions (pda), both of which possess binding capability to metals The combination of this redox behavior and complexation with transition metals is expected to provide an efficient redox system 1,2-Benzoquinonediimines have received extensive interest as a redox- active ligand in this context [4] However, transition-metal complexes with 1,4-benzoquinonediimine have been investigated... is a promising approach to an architecturally controlled formation of redox- active conjugated polymeric or macrocyclic complexes with 1,4-benzoquinonediimines 1 Conjugated Complexes with Quinonediimine Derivatives 5 This chapter sketches an outline of conjugated complexes with redox- active π-conjugated qd derivatives, including redox properties and structures of the conjugated complexes 1.2 Architecturally... metals This valence isomerization is considered to depend on the redox properties of both components Vanadium compounds can exist in a variety of oxidation states and generally convert between the states via a one-electron redox process [17] Vanadium compounds in low oxidation states can serve as one-electron reductants, as exemplified by the redox 1 Conjugated Complexes with Quinonediimine Derivatives . meso-Tetrakis(4-carboxyphenyl)porphyrin (TCPP) 267 16.2.2 Photoinduced Electron Transfer from a Porphyrin toanElectronAcceptorinanAntibody-CombiningSite 273 16.3 Peroxidase Activity of Fe-Porphyrin-Antibody Complexes. design & production GmbH, Heidelberg Typesetting and production: LE-T E X J elonek, Schmidt & Vöckler GbR, Leipzig Printed on acid-free paper 2/3141/YL - 5 4 3 2 1 0 springer.com Redox Systems. metallic dopant to form a multiredo x and multimetallic system. Conjugated complexes provide redox- switching systems based on redox properties of the qd spacer. Abbreviations bpy 2,2  -Bipyridine CD