Synthesis of a new donor, MOET‐TTP, and the crystal structure, electrical, and magnetic properties of (MOET‐TTP)2MCl4 (M = Fe and Ga)

Takashi Shirahata, Tetsuya Ito, Shinya Toki, Yohji Misaki

doi:10.1002/pssb.201100674

<jats:title>Abstract</jats:title><jats:p>A new 2,5‐bis(1,3‐dithiol‐2‐ylidene)‐1,3,4,6‐tetrathiapentalene (BDT‐TTP) type donor, 2‐(4,5‐dimethoxy‐1,3‐dithiol‐2‐ylidene)‐5‐(4,5‐ethylenedithio‐1,3‐dithiol‐2‐ylidene)‐1,3,4,6‐tetrathiapentalene (MOET‐TTP) was synthesized and its magnetic and non‐magnetic anion salts (MOET‐TTP)<jats:sub>2</jats:sub><jats:italic>M</jats:italic>Cl<jats:sub>4</jats:sub> (<jats:italic>M</jats:italic> = Fe and Ga), were prepared. These salts are isostructural and belong to the space group of <jats:italic>P</jats:italic>1. They show metal‐like behavior down to 200 K for the FeCl<jats:sub>4</jats:sub> salt and 20 K for the GaCl<jats:sub>4</jats:sub> salt. The band structures of these salts are two‐dimensional. The <jats:italic>M</jats:italic>Cl<jats:sub>4</jats:sub> anions are located between the donor columns and close to the ethylenedithio and methoxy groups of the donor molecules. The magnetic susceptibilities of the FeCl<jats:sub>4</jats:sub> salts follow the Curie–Weiss law with Curie constant of 4.3 emu K mol<jats:sup>−1</jats:sup> and Weiss temperature of <jats:italic>θ</jats:italic> = −1.8 K, revealing a weak antiferromagnetic interaction of 3d spins of the FeCl<jats:sub>4</jats:sub> anions. The <jats:styled-content>${\rm Fe}\cdots {\rm Fe}$<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-ueqn-1.gif" xlink:title="equation image" /></jats:styled-content> (6.508(3) Å) and <jats:styled-content>${\rm Cl}\cdots {\rm Cl}$<jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/tex2gif-ueqn-2.gif" xlink:title="equation image" /></jats:styled-content> (3.78–4.69 Å) distances in the crystal structure of the salt are significantly long. Therefore, the direct magnetic interaction between the 3d spins of the nearest neighboring Fe<jats:sup>3+</jats:sup> ions does not seem readily accessible.</jats:p>

Synthesis of a new donor, MOET‐TTP, and the crystal structure, electrical, and magnetic properties of (MOET‐TTP)<sub>2</sub><i>M</i>Cl<sub>4</sub> (<i>M</i> = Fe and Ga)

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