1009-13-8Relevant academic research and scientific papers
Stepwise formation of quasi-octahedral macrocyclic complexes of rhodium(III) and iridium(III) bearing a pentamethylcyclopentadienyl group
Yamamotoa, Yasuhiro,Suzuki, Hajime,Tajima, Nobuo,Tatsumi, Kazuyuki
, p. 372 - 379 (2002)
Reactions of [{MCl2(Cp*)}2] (1: M=Ir, 2: M=Rh) with bidentate ligands (L) such as 1,4-diisocyano-2,5-dimethylbenzene (a), 1,4-diisocyano-2,3,5,6-tetramethylbenzene (b), pyrazine (c) or 4,4′-dipyridyl (d) gave the corresponding dinuclear complexes [{MCl2(Cp*)}2(L)] (M=Ir: 3a, 3b, 5c, 5d; M=Rh: 4b, 6c, 6d), which were converted into tetranuclear complexes [{M2 (μ-Cl)2(Cp*)2} 2(L)2](OTf)4 (M=Ir: 7c, 7d, 9a, 9b; M=Rh: 8c, 8d, 10b) on treatment with Ag(OTf). X-ray analyses of 8c and 8d revealed that each of four pentamethylcyclopentadienyl metal moieties was connected by two μ-Cl-bridged atoms and a bidentate ligand to construct a rectangular cavity with the dimensions of 3.7 × 7.0 A for 8c and 3.7 × 11.5 A for 8d. Both the Rh2Cl2 and pyrazine (or 4,4′dipyridyl) ring planes are perpendicular to the Rh4 plane. Treatment of Cl-bridged complexes (7c, 7d, 8c, 8d, 9b, and 10b) with a different ligand (L') resulted in cleavage of the Cl bridges to produce two-dimensional complexes [{MCI(Cp*)}4{(L)-(L')}2](OTf)4 (11ac, 11bc, 11bd, 12bc, and 12bd) with two different ligand edges . Complex 10b reacted readily with 1,4-diisocyano-2,3,5,6-tetramethyl-benzene (b) to give a tetranuclear rhodium(III) complex 12bb. The structure of tetranuclear complexes was confirmed by X-ray analysis of 11bc. Each {(MCp*} moiety is surrounded by a Cl atom, isocyanide, and pyrazine (or 4,4′-dipyridyl) and the dimensions of its cavity are 7.0 × 11.6 A.
Synthesis, characterization and mechanochromic behavior of binuclear gold (I) complexes with various diisocyano bridges
Liang, Jinhua,Hu, Fang,Lv, Xiaoyi,Chen, Zhao,Chen, Zhiming,Yin, Jun,Yu, Guang-Ao,Liu, Sheng Hua
, p. 485 - 490 (2012/10/30)
A series of binuclear gold (I) complexes were synthesized. Their structures were characterized by elemental analyses, IR spectrometry, UV-Vis spectroscopy and single crystal X-ray diffraction. Their fluorescent mechanochromic (tribochromic) properties were investigated. The results of the mechanochromic studies suggested that the gold complexes with methylsubstituted phenyl bridges exhibited mechanochromism and a 100 nm red-shift of fluorescent spectrum could be observed after grinding. The complex with a diphenylmethane bridge exhibited mechanochromism with a change in fluorescence from green to blue (25 nm red-shift after grinding). The ground complexes reverted to their original states by treatment with CH2Cl2. No mechanochromism was observed for either the biphenyl or diphenylethane containing complexes.
