Continuous Control of Optical Gaps in Quasi-One-Dimensional Bromide-Bridged Platinum Complexes by Utilizing Chemical Pressure

详细信息    查看全文

• 作者：Shohei Kumagai ; Hiroaki Iguchi ; Shinya Takaishi ; Brian K. Breedlove ; Masahiro Yamashita ; Hiroyuki Matsuzaki ; Hiroshi Okamoto ; Kenichi Kato ; Masaki Takata
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 3, 2014
• 年：2014
• 卷：53
• 期：21
• 页码：11764-11769
• 全文大小：420K
• ISSN：1520-510X

文摘

The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)₂Br](C_n鈥揧)₂路H₂O (en = ethylenediamine; C_n鈥揧 = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)₂Br](C₆鈥揧)₂路H₂O is in a mixed-valence state at 200 K. In addition, Pt鈥揚t distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt鈥揚t distance was quite short. This is probably because of the energetic mismatch between 5d_z² orbitals of the Pt ions and 4p_z orbitals of the Br ions.