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Halido‐Bridged 1D Mixed‐Valence Cu I –Cu II Coordination Polymers Bearing a Piperidine‐1‐carbodithioato Ligand: Crystal Structure, Magnetic and Conductive Properties, and Application in Dye‐Sensitized Solar Cells
Author(s) -
Tanaka Naoya,
Okubo Takashi,
Anma Haruho,
Kim Kyung Ho,
Inuzuka Yoshie,
Maekawa Masahiko,
KurodaSowa Takayoshi
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300188
Subject(s) - chemistry , copper , crystallography , dithiocarbamate , valence (chemistry) , crystal structure , antiferromagnetism , acetonitrile , ligand (biochemistry) , magnetic susceptibility , piperidine , unpaired electron , stereochemistry , molecule , organic chemistry , biochemistry , receptor , condensed matter physics , physics
New mixed‐valence Cu I –Cu II 1D coordination polymers of the structure [Cu I 2 Cu II X 2 (Pip‐dtc) 2 (CH 3 CN) 2 ] n [Pip‐dtc = piperidine‐1‐carbodithioate; X = Br ( 1a ), I ( 1b )] containing a dithiocarbamate derivative have been synthesized and structurally characterized by X‐ray diffraction. The 1D infinite chains were formed from mononuclear copper units [Cu(Pip‐dtc) 2 ] connected by bromido‐ or iodido‐bridged copper dinuclear units that include acetonitrile ligands {i.e., [Cu 2 X 2 (CH 3 CN) 2 ]}. Evaluation of the magnetic properties of 1a and 1b revealed that these complexes displayed relatively strong antiferromagnetic interactions [ J = –20.4 cm –1 ( 1a ) and J = –18.8 cm –1 ( 1b )] between unpaired electrons of the copper(II) ions through the dinuclear halido–copper(I) units. Impedance spectroscopy revealed that complexes 1a and 1b exhibit intriguing semiconducting properties at activation energies of E a = 0.78 eV ( 1a ) and E a = 0.62 eV ( 1b ). Coordination polymers 1a and 1b were then adopted as the sensitizing material in dye‐sensitized solar cells (DSSCs).