Creation of multi-dimensional structures of functional molecules by metal complexation reactions

本研究旨在利用过渡金属络合物的络合反应构建新的多维功能分子体系。目前研究的分子体系有：1)具有光功能的偶氮共轭金属络合物；2)具有质子耦合分子内电子转移反应能力的给体-受体共轭络合物；3)氧化还原和光功能络合物修饰的金属纳米粒子。结果表明，偶氮二茂铁的反式-顺式异构化反应不仅通过光激发π-π^*跃迁进行，也通过光激发MLCT(d-π^*跃迁)进行。结合单一紫外光照射和Co(II)和Co(III)之间的可逆氧化还原变化，可以可逆地改变偶氮苯-联吡啶配体钴配合物中的反式/顺式比值。新合成的镍、钯、铂对甲基偶氮苯二硫醇c-…更多的复合体2-4表现出可逆的反式-顺式光致异构化、原色性和新型的质子耦合顺式-反式异构化。1-二茂铁乙叉并[1]-二茂铁乙叉并[1]-[2]-[2]-[1]-[1]-[2]-[1]-[2][1]-[2][1][1][1][1][2][1][1][1][1][2][1][1][1]，[1][1][1][1][1][1][1][1][1][1][1][1][1][1][2][1][1][2][1][2]][2][2]，[2]，[2]，[一个2：1的供体-受体络合物，L，5-二(二茂铁乙炔基)-5-二(二茂铁乙炔基)蒽醌经历了两步质子反应，双质子化物种包括η^6-富烯-Fe(II)络合物-异丁烯结构，以及溶液中二茂铁(Fe(III))离子和半醌自由基自旋分离的新形式。此外，该络合物在固态下处于给体-受体体系的价异构体之间的热平衡状态。研究了双二茂铁和蒽醌衍生物修饰的Au和Pd簇合物的合成和电化学沉积行为。还可以通过交替电沉积BFC修饰的金和钯纳米颗粒来制备异质结构。较少

To construct new multi-dimensional functional molecular systems by utilizing complex reactions of transition metal complexes has been investigated in this research project. The molecular systems that have been focused are 1) azo-conjugated metal complexes with photo-functions, 2) donor-acceptor conjugated complexes with an ability of proton-coupled intramolecular electron-transfer reactions, and 3) metal nanoparticles modified with redox- and photo-functional complexes. The summary of the results is as follows.The trans-to-cis isomerization of azoferrocene proceeds not only by the photoexcitation of the π-π^* transition band but also by photoexcitation of the MLCT (d-π^* transition) band. The trans/cis ratio of the azobenzene-attached bipyridine ligands in their cobalt complex is reversibly altered by a combination of photoirradiation with a single UV light source and the reversible redox change between Co(II) and Co(III). A newly synthesized Ni, Pd and Pt tolylazophenylenedithiolato c … More omplexes 2-4 show reversible trans-to-cis photoisomerization, proto-chromism, and novel proton-coupled cis-to-trans isomerization.The protonation to carbonyl groups of the anthraquinone moiety in 1 -ferrocenylethynylanthraquinone causes intramolecular electron transfer leading to a novel structural change into a η^6-fulvene-cumulene Fe(II) complex. A 2:1 donor-acceptor complex, l,5-bis(ferrocenylethynyl)anthraquinone undergoes a two-step proton response, and the doubly protonated species involves a η^6-fulvene-Fe(II) complex-cumulene structure, and a novel spin-separated form of a ferrocenium (Fe(III)) ion and a semiquinone radical in the solution. Furthermore, the complex is in a thermal equilibrium between the valence tautomers of a donor-acceptor system in the solid state.Synthesis and electrochemical deposition behavior of biferrocene and anthraquinone derivative-modified Au and Pd clusters have been investigated. It is also possible to fabricate hetero structures by alternative electrodeposition of Bfc-modified gold and palladium nanoparticles. Less