single-component charge-transfer crystals based on spin-carrying tcnq (7,7,8,8-tetracyanoquinodimethane) derivatives单组分电荷转移水晶基于spin-carrying tcnq(7、8、8-tetracyanoquinodimethane)衍生品.pdf

Crystals 2012, 2, 662-668; doi:10.3390/cryst2020662 OPEN ACCESS crystals ISSN 2073-4352 /journal/crystals Article Single-Component Charge-Transfer Crystals Based on Spin-Carrying TCNQ (7,7,8,8-Tetracyanoquinodimethane) Derivatives Hideto Suzuki, Hiroki Akutsu, Jun-ichi Yamada and Shin’ichi Nakatsuji * Graduate School of Material Science, University of Hyogo, 3-2-1 Kouto, Kamigori, Hyogo 678-1297, Japan; E-Mails: suzuki_hidemaru@yahoo.co.jp (H.S.); akutsu@sci.u-hyogo.ac.jp (H.A.); yamada@sci.u-hyogo.ac.jp (J.Y.) * Author to whom correspondence should be addressed; E-Mail: nakatuji@sci.u-hyogo.ac.jp; Tel.: +81-791-58-0163; Fax: +81-791-58-0164. Received: 16 March 2012; in revised form: 1 June 2012 / Accepted: 5 June 2012 / Published: 12 June 2012 Abstract: Three TCNQ derivatives carrying nitroxide radicals (3a–3c) were prepared and were found to form single-component charge-transfer (CT) complexes by self-assembly, in which outer nitroxide groups of a couple of different molecules work as donors and the inner TCNQ unit of another molecule as an acceptor. While the CT interactions found for the TEMPO (2,2,6,6-tetramethylpiperidin-1-oxy) derivative 3a and the PROXYL (2,2,5,5-tetramethylpirrolidin-1-oxy) derivative 3b are point-to-face fashion between the oxygen atom of each nitroxide group and the six-membered ring of inner TCNQ unit, the CT interactions found for the PO (2,2,5,5-tetramethyl-3-pyr