Journal of the American Chemical Society
Page 6 of 10
1
2
3
4
5
6
7
8
9
(5) (a) Campbell, M. G.; Powers, D. C.; Raynaud, J.; Graham, M. J.;
Xie, P.; Lee, E.; Ritter, T. Nature Chem. 2011, 3, 949. (b) Campbell, M.
G.; Zheng, S.ꢀL.; Ritter, T. Inorg. Chem. 2013, 52, 13295.
(6) Takaishi, S.; Takamura, M.; Kajiwara, T.; Miyasaka, H.; Yamaꢀ
shita, M.; Iwata, M.; Matsuzaki, H.; Okamoto, H.; Tanaka, H.; Kuroda,
S.; Nishikawa, H.; Oshio, H.; Kato, K.; Takata, M. J. Am. Chem.
Soc. 2008, 130, 12080.
(7) Kumagai, S.; Takaishi, S.; Breedlove, B. K.; Okamoto, H.; Tanaka,
H.; Kuroda, S.; Yamashita, M. Chem. Commun. 2014, 50, 8382.
(8) (a) Toriumi, K.; Wada, Y.; Mitani, T.; Bandow, S.; Yamashita, M.;
Fujii, Y. J. Am. Chem. Soc. 1989, 111, 2341. (b) Kishida, H.; Matsuzaki,
H.; Okamoro, H.; Manabe, T.; Yamashita, M.; Taguchi, Y.; Tokura, Y.
Nature 2000, 405, 929. (c) Iwai, S.; Ono, M.; Maeda, A.; Matsuzaki, H.;
Kishida, H.; Okamoto, H.; Tokura, Y. Phys. Rev. Lett. 2003, 91, 057401.
(d) Takaishi, S.; Tobu, Y.; Kitagawa, H.; Goto, A.; Shimizu, T.; Okubo,
T.; Mitani, T.; Ikeda, R. J. Am. Chem. Soc. 2004, 126, 16145. (e) Takaishi,
S.; Yamashita, M.; Matsuzaki, H.; Okamoto, H.; Tanaka, H.; Kuroda, S.;
Goto, A.; Shimizu, T.; Takenobu, T.; Iwasa, Y. Chem. Eur. J. 2008, 14,
472.
shorten d(Pd–Br–Pd) and prepare stable and highly conductive
Pd(III)Br chains.
In conclusion, a new synthetic method to obtain PdBr chain
complexes with the Pd ions in an uncommon Pd(III) oxidation
state was reported. [Pd(dabdOH)2Br]Br2 (3) was designed to conꢀ
tain additional hydrogen donor groups (hydroxy group) in the inꢀ
plane ligand. The hydroxy groups form hydrogen bonds with the
counteranions (Br(Y)) in addition to the hydrogen bonds between
the amino groups and Br(Y). Our method is significant for three
reasons. First, 3 has the shortest d(Pd–Br–Pd) of all the reported
PdBr chains to date, and thus, the Pd(III) state is stabilized up to
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
the decomposition temperature (443 K). Second, σ
RT of 3 was 106
times higher than that of other PdBr chains (3–38 S cm–1), making
3 the most conducting MX chains so far reported. Third, the prisꢀ
matic crystals of 3 are robust enough to endure optical and physiꢀ
cal property measurements. Further studies on the intrinsic physiꢀ
cal properties of the 1D electron system are currently underway.
Precise positional control of ions via multiple hydrogenꢀbond
networks is applicable to other molecular crystals, e.g., Pt(III)X
chains, which may exhibit metallic conductivity and have a
unique 1D electron system.
(9) Kimizuka, N. Adv. Polym. Sci. 2008, 219, 1.
(10) (a) Kawakami, D.; Yamashita, M.; Matsunaga, S.; Takaishi, S.;
Kajiwara, T.; Miyasaka, H.; Sugiura, K.; Matsuzaki, H.; Okamoto, H.;
Wakabayashi, Y.; Sawa, H. Angew. Chem., Int. Ed. 2006, 45, 7214. (b)
Kobayashi, A.; Kitagawa, H. J. Am. Chem. Soc. 2006, 128, 12066. (c)
Otsubo, K.; Kobayashi, A.; Sugimoto, K.; Fujiwara, A.; Kitagawa, H.
Inorg. Chem. 2014, 53, 1229. (d) Hashiguchi, R.; Otsubo, K.; Maesato,
M.; Sugimoto, K.; Fujiwara, A.; Kitagawa, H. Angew. Chem., Int. Ed.
2017, 56, 3838.
(11) Otsubo, K.; Kitagawa, H. CrystEngComm. 2014, 16, 6277.
(12) (a) Otsubo, K.; Wakabayashi, Y.; Ohara, J.; Yamamoto, S.;
Matsuzaki, H.; Okamoto, H.; Kitagawa, H. Nat. Mater. 2011, 10, 291. (b)
Otake, K.; Otsubo, K.; Sugimoto, K.; Fujiwara, A.; Kitagawa, H. Angew.
Chem. Int. Ed. 2016, 55, 6448.
ASSOCIATED CONTENT
Supporting Information
Additional experimental details for the synthesis and characterizaꢀ
tion in pdf file and Xꢀray crystallographic information file in CIF
format. This material is available free of charge via the Internet at
(13) (a) Yamashita, M.; Takaishi, S. Chem. Commun. 2010, 46, 4438.
(b) Kumagai, S.; Takaishi, S.; Iguchi, H.; Yamashita, M. Dalton Trans.
2015, 44, 8590.
AUTHOR INFORMATION
Corresponding Author
(14) (a) Mash, E. A.; Nelson, K. A.; Van Deusen, S.; Hemperly, S. B.;
Theisen, P. D.; Heathcock, C. H. Org. Synth. 1990, 68, 92. (b) Scheurer,
A.; Mosset, P.; Saalfrank, R. W. Tetrahedron: Asymmetry 1997, 8, 1243.
(15) Interrante, L. V.; Browall K. W. Inorg. Chem. 1974, 13, 1162.
(16) (a) Takaishi, S.; Miyasaka, H.; Sugiura, K.; Yamashita , M.;
Matsuzaki, H.; Kishida, H., Okamoto, H.; Tanaka, H.; Marumoto, K.; Ito,
H.; kuroda, S.; Takami, T. Angew. Chem. Int. Ed. 2004, 43, 3171. (b)
Takaishi, S.; Kawakami, D.; Yamashita, M.; Sasaki, M,; Kajiwara, T.;
Miyasaka, H.; Okamoto, H.; watanabe, H.; Tanaka, H.; Marumoto, K.; Ito,
H.; kuroda, S. J. Am. Chem. Soc., 2006, 128, 6420. (c) Hoshimi, Y.; Yoꢀ
shida, S.; Taninaka, A.; Yoshida, T.; Takaishi, S.; Takeuchi, O.; Yamashiꢀ
ta, M.; Shigekawa, H. Jpn. J. Appl. Phys. 2016, 55, 08NB16.
(17) Cox, P. A. The Electronic Structure and Chemistry of Solids; Oxꢀ
ford University Press: New York,1987, Chapter 5.
*hꢀiguchi@m.tohoku.ac.jp (H.I.)
*yamasita@agnus.chem.tohoku.ac.jp (M.Y.).
ORCID
Hiroaki Iguchi: 0000ꢀ0001ꢀ5368ꢀ3157
Shinya Takaishi: 0000ꢀ0002ꢀ6739ꢀ8119
Notes
The authors declare no competing financial interests.
(18) Interrante, L. V.; Browall, K. W.; Bundy, F. P. Inorg. Chem. 1974,
13, 1158.
ACKNOWLEDGMENT
(19) (a) Mitsumi, M.; Kitamura, K.; Morinaga, A.; Ozawa, Y.; Kobaꢀ
yashi, M.; Toriumi, K.; Iso, Y.; Kitagawa, H.; Mitani, T. Angew. Chem.
Int. Ed. 2002, 41, 2767. (b) Iguchi, H.; Takaishi, S.; Yamashita, M. Chem.
Lett. 2014, 43, 69. (c) Otsubo, K.; Suto, T.; Kobayashi, A.; Ikeda, R.;
Hedo, M.; Uwatoko, Y.; Kitagawa, H. Eur. J. Inorg. Chem. 2016, 4402.
(20) Tadokoro, M.; Yasuzuka, S.; Nakamura, M.; Mitsumi, M.; Ozawa,
Y.; Toriumi, K.; Yoshino, H.; Shiomi, D.; Sato, K.; Takui, T.; Mori, T.;
Murata, K. Angew. Chem. Int. Ed. 2006, 45, 5144.
(21) Hendon, C. H.; Walsh, A.; Akiyama, N.; Konno, Y.; Kajiwara, T.;
Ito, T.; Kitagawa, H.; Sakai, K. Nature Commun. 2016, 7, 11950.
(22) Zeller, H. R.; Beck, A. J. Phys. Chem. Solids, 1974, 35, 77.
(23) Cox, P. A. The Electronic Structure and Chemistry of Solids; Oxꢀ
ford University Press: New York, 1987, p100.
(24) Sasaki, M.; Wu, H.; Kawakami, D.; Takaishi, S.; Kajiwara, T.;
Miyasaka, H.; Breedlove, B. K.; Yamashita, M.; Kishida, H.; Matsuzaki,
H.; Okamoto, H.; Tanaka, H.; Kuroda, S. Inorg. Chem. 2009, 48, 7446.
(25) Yoshida, T.; Takaishi, S.; Iguchi, H.; Okamoto, H.; Tanaka, H.;
Kuroda, S.; Hosomi, Y.; Yoshida, S.; Shigekawa, H., Kojima, T.; Ohtsu,
H., Kawano, M., Breedlove, B. K.; Guérin, L.; Yamashita, M. Chemis-
trySelect 2016, 1, 259.
This work was partly supported by JSPS KAKENHI Grant Numꢀ
bers JP15K17828 (H.I.), JP26248015 (M.Y.), by the Sumitomo
Foundation (H.I.), by the CASIO Science Promotion Foundation
(H.I.), by the Ogasawara Foundation for the Promotion of Science
and Engineering (H.I.), by the Program for Interdisciplinary Reꢀ
search in Tohoku University Frontier Research Institute for Interꢀ
disciplinary Sciences (H.I.), and CREST, JST (H.I., M.Y. and
H.O.).
REFERENCES
(1) Cotton, F. A.; Gu, J.; Murillo, C. A., Timmons, D. J. J. Am. Chem.
Soc. 1998, 120, 13280.
(2) (a) Powers, D. C.; Ritter, T.; Nature Chem. 2009, 1, 302. (b) Powꢀ
ers, D. C.; Ritter, T. Acc. Chem. Res. 2012, 45, 840.
(3) Khusnutdinova, J. R.; Rath, N. P.; Mirica, L. M. Angew. Chem. Int.
Ed. 2011, 50, 5532.
(4) Mirica, L. M.; Khusnutdinova, J. R. Coord. Chem. Rev. 2013, 257,
299.
ACS Paragon Plus Environment