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Quintuple-Decker Heteroleptic Phthalocyanine Heterometallic Samarium-Cadmium Complexes. Synthesis, Crystal Structure,
Chao Liu1, Wei Yang1, Yuexing Zhang2
1Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Abstract:
A one-pot synthesis methodology was employed for obtaining diverse quintuple-decker phthalocyanine heterometallic lanthanide-cadmium complexes. By using the reaction of a double-decker homoleptic/heteroleptic phthalocyanine samarium compound with metal-free phthalocyanine and cadmium acetate in 1,2,4-trichlorobenzene at 200 °C, two novel quintuple-decker heteroleptic phthalocyanine heterometallic samarium-cadmium compounds, {(Pc)Sm(Pc)Cd(Pc*)Cd(Pc)Sm(Pc)} (1) and {(Pc)Sm(Pc*)Cd(Pc*)Cd(Pc*)Sm(Pc)} (2), together with one homoleptic phthalocyanine species, {(Pc*)Sm(Pc*)Cd(Pc*)Cd(Pc*)Sm(Pc*)} (3), were successfully fabricated, where H2Pc and H2Pc* represent unsubstituted phthalocyanine and 2,3,9,10,16,17,23,24-octakis(n-pentyloxy)phthalocyanine, respectively. Their quintuple-decker structures have been disclosed by various spectroscopic techniques and single-crystal X-ray diffraction. In addition, valence tautomerization of these three quintuple-decker complexes has been achieved by the addition of phenoxathiin hexachloroantimonate, giving three oxidized forms including one-, two-, and three-electron oxidation products. From 1 to 3 with the same oxidation state, the increased number of n-pentyloxy substituents of phthalocyanine ligands induces the blue shift of electronic absorption in the IR region due to the increased gap associated with the introduction of electron-donating substituents. In particular, the electronic absorption spectra of one- and two-electron oxidation products for 1 exhibit a rare band in the middle-IR region around 3000 nm, being one of the farthest electronic transitions captured by UV-vis spectroscopy. The three-electron oxidation product of 1 displays two bands at 2231 and 2740 nm, respectively. These data are well confirmed by IR spectroscopic data and theoretical calculation results.
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