Mixed cyclic tetramerization of 5,6-dicyano-2-(4,5-bis(amylthio)-1,3-dithio-2-ylidene)-benzo[d]-1,3-dithiole and 1,2-dicyanobenzene with half-sandwich complex Eu(Pc)(acac) as template in the presence of DBU in refluxing n-pentanol led to the formation and isolation of a series of unprecedented tetrathiafulvalene(TTF)-fused heteroleptic bis(phthalocyaninato) europium double-deckers Eu(Pc)[Pc(TTF)_n] (n = 1–4) (1, 2-cis, 2-trans, 3, and 4). Electronic absorption spectroscopic results reveal the effect of fusing TTF onto the phthalocyanine chromophore of double-decker on the electronic structure of the target compounds. ESR together with the IR and electronic absorption spectra disclose the existence of unpaired electron in the newly prepared heteroleptic complexes. In particular, in addition to the Pc-chromophore based one-electron redox processes, one-electron, two-electron, three-electron, and four electron oxidation processes were clearly revealed by the electrochemical technique for the one-TTF, two-TTF, three-TTF, and four-TTF moiety-fused double-decker 1, 2-cis and 2-trans, 3, and 4, respectively, indicating the significant influence of the TTF moieties fused to the double-decker electronic structure. In particular, theoretical calculations over 0 and 4 in combination with the electronic absorption spectroscopy reveal the significant influence of the fused-TTF units to the electronic structure.

5,6-二氰基-2-（4,5-双（戊硫基）-1,3-二硫-2-亚基）-苯并[ d ] -1,3-二硫醇和1,2-二氰基苯的混合环四聚半三明治复合物Eu（Pc）（acac）在DBU存在下在正戊醇回流中作为模板，导致形成和分离了一系列前所未有的四硫富富瓦烯（TTF）熔合的杂配双（邻酞菁）double双层（PC）[PC（TTF）_ñ ]（N = 1-4）（1，2-顺，2-反式，3，和4）。电子吸收光谱结果揭示了将TTF融合到双层酞菁生色团上对目标化合物电子结构的影响。ESR与红外光谱和电子吸收光谱一起揭示了新制备的杂配配合物中存在不成对的电子。特别地，除了基于Pc-发色团的单电子氧化还原过程外，通过电化学技术还清楚地揭示了单TTF，两TTF的一电子，二电子，三电子和四电子氧化过程。三TTF，以及四个-TTF部分稠合的双层1，2-顺式和2-反式，3，和4分别表示融合了双层电子结构的TTF部分的重大影响。特别是，结合电子吸收光谱对0和4进行的理论计算揭示了TTF熔融单元对电子结构的重大影响。