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Packing Motifs and Magneto‐Structural Correlations in Crystal Structures of Metallo‐Tetrakis(1,2,5‐thiadiazole)porphyrazine Series, MTTDPz (M=H 2 , Fe, Co, Ni, Cu, Zn)
Author(s) -
Suzuki Yosuke,
Fujimori Masato,
Yoshikawa Hirofumi,
Awaga Kunio
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400394
Subject(s) - porphyrazine , crystallography , stacking , sublimation (psychology) , phthalocyanine , crystal structure , metal , materials science , chemistry , nanotechnology , polymer chemistry , psychology , organic chemistry , psychotherapist , metallurgy
Single crystals of tetrakis(thiadiazole)porphyrazine and the corresponding metal( II ) derivatives, MTTDPz (M=H 2 , Fe, Co, Ni, Cu, and Zn) were grown by sublimation under reduced pressure with continuous N 2 gas flow. Their structures, obtained by X‐ray crystallographic analysis, depend significantly on the central metal ion, and the M=Ni and Cu derivatives exhibit polymorphism. They can be classified into three forms, α, β, and γ. The α form (M=H 2 , Ni, and Cu) is composed of two‐dimensional hexagonal close packing formed by side‐by‐side contacts between thiadiazole rings, whereas the β form (M=Fe, Co, and Zn) crystallizes into a one‐dimensional coordination polymer. The γ form (M=Ni and Cu) consists of a ladder structure caused by π stacking, similar to the β form of phthalocyanine, and by side‐by‐side contacts between thiadiazole rings. Although the crystal structures of the MTTDPz series exhibited multi‐dimensional network structures, magnetic measurements revealed relatively weak exchange interactions, probably reflecting the long distances between the metal ions.