Syntheses and Unusual Segregated-Alternated Hybrid Stacking Structure of Hydrogen-Bonded Charge-Transfer Complexes Composed of Bis[2,3-pyridinedithiolate]metal Complexes

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• 作者：Sota Shibahara ; Hiroshi Kitagawa ; Yoshiki Ozawa ; Koshiro Toriumi ; Takashi Kubo ; Kazuhiro Nakasuji
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：February 19, 2007
• 年：2007
• 卷：46
• 期：4
• 页码：1162 - 1170
• 全文大小：324K
• 年卷期：v.46,no.4(February 19, 2007)
• ISSN：1520-510X

文摘

We report the syntheses of new planar electron donor inorganic molecules [bis(2,3-pyridinedithiolate)metal(II)];[M^II(Hpydt)₂] (M = Ni(1), Pd(2), Pt(3)) and their anions; [M^II(pydt)₂]^2- (M = Ni(4), Pd(5)), which are equipped withboth a highly lying highest occupied molecular orbital (HOMO) perpendicular to the plane and hydrogen-bondingcapability in the plane. In addition, we present two novel hydrogen-bonded charge-transfer (HBCT) complexes,[M(Hpydt)₂]TCNQ (M = Ni, Pd), with 7,7,8,8-tetracyanoquinodimethane (TCNQ). All the neutral and ionic inorganicmolecules and the HBCT complexes were successfully characterized by single-crystal X-ray crystallography. TheHBCT complexes show an unusual segregated-alternated hybrid stacking structure in which each componentinteracts parallel to the stacks with neighboring donors and acceptors. Furthermore, the structural network is expandedas a result of a one-dimensional hydrogen-bonding chain formed between donors and acceptors perpendicular tothe stacking direction. The theoretical electronic structures of the HBCT complexes are also reported.