Inorganic Chemistry
Communication
potentials for the tricyanide building blocks (E1/2 = −0.79 for Tp
vs −0.80 mV for MeTp).5g,10 Second, as mentioned in the X-ray
structure, compound 1·2MeOH has highly bent ∠Co−NC
angles and a distorted {Fe2(μ-CN)4Co2} core, which will hinder
the effective formation of σ and π bonds of Co−NCN and
markedly impair electron delocalization of the molecule through
the CoII centers. As a result, more charge on the bridging
cyanides will weaken their π acceptance, enhance Fe → CN π-
back-donation, lead to CN bond weakening and a
concomitant lowering of νCN, and give lower redox potentials
of Fe centers (lower transition temperature). In fact, we did
observe the much smaller value of νCN in 1·2MeOH. For the
analogues of complex 1 and the desolvated form of 2·2MeOH
(2),5e the ∠Co−NC angles and the stretching vibration of the
bridging cyanides are 150.9(3) and 148.4(3)° and 2143 cm−1 for
1 and 174.4(9) and 179.2(12)° and 2168 cm−1 for the latter,5e
respectively. The remarkable red shift of νCN for 1 should be
attributed to distortion of the FeIII−CN−CoII linkages. More-
over, different from 1, complex 2 displays CTIST below 250 K.5e
The facts indicate that the bent ∠Co−NC angles and
distortion of the {Fe2(μ-CN)4Co2} core are the key factors for
lowering of the transition temperature in 1·2MeOH and 1
compared to its analogues.
Hysteresis loops are found in the family of complex 1·2MeOH,
while complex 2 shows a crossover behavior and no hysteresis.5e
It is believed that the cooperativity of intermolecular elastic
interactions can lead to first-order phase transition and
hysteresis.5b Structure analysis indicates that there are no
effective intermolecular π−π-stacking interactions between the
bipyridine rings in the structures of 1·2MeOH, 1, and 1·
2CD3OD. However, rather strong nonclassical hydrogen bonds
(C−H···O) were found in these compounds between the
carbonyl O atoms (O1 and O7) and the adjacent C atoms (C28
REFERENCES
■
(1) Sato, O.; Iyoda, T.; Fujishima, A.; Hashimoto, K. Science 1996, 272,
704−705.
(2) (a) Halcrow, M. A.; Dunbar, K. R.; Achim, C.; Shatruk, M. Charge
Transfer-Induced Spin-Transitions in Cyanometalate Materials; Wiley:
New York, 2013. (b) Sato, O.; Tao, J.; Zhang, Y.-Z. Angew. Chem., Int.
Ed. 2007, 46, 2152−2187.
(3) For example: (a) Bleuzen, A.; Lomenech, C.; Escax, V.; Villain, F.;
Varret, F.; Cartierdit Moulin, C.; Verdaguer, M. J. Am. Chem. Soc. 2000,
122, 6648−6652. (b) Arimoto, Y.; Ohkoshi, S.; Zhong, Z. J.; Seino, H.;
Mizobe, Y.; Hashimoto, K. J. Am. Chem. Soc. 2003, 125, 9240−9241.
(c) Cafun, J. D.; Champion, G.; Arrio, M. A.; dit Moulin, C. C.; Bleuzen,
A. J. Am. Chem. Soc. 2010, 132, 11552−11559.
(4) (a) Berlinguette, C. P.; Dragulescu-Andrasi, A.; Sieber, A.; Galan
́
-
Mascaros, J. R.; Gudel, H.-U.; Achim, C.; Dunbar, K. R. J. Am. Chem. Soc.
́
̈
2004, 126, 6222−6223. (b) Berlinguette, C. P.; Dragulescu-Andrasi, A.;
Sieber, A.; Gudel, H.-U.; Achim, C.; Dunbar, K. R. J. Am. Chem. Soc.
̈
2005, 127, 6766−6779. (c) Hilfiger, M. G.; Chen, M.; Brinzari, T. V.;
Nocera, T. M.; Shatruk, M.; Petasis, D. T.; Musfeldt, J. L.; Achim, C.;
Dunbar, K. R. Angew. Chem., Int. Ed. 2010, 49, 1410−1413.
(d) Avendano, C.; Hilfiger, M. G.; Prosvirin, A.; Sanders, C.; Stepien,
D.; Dunbar, K. R. J. Am. Chem. Soc. 2010, 132, 13123−13125. (e) Funck,
K. E.; Prosvirin, A. V.; Mathonier
Chem. 2011, 50, 2782−2789.
(5) (a) Li, D.-F.; Clerac, R.; Roubeau, O.; Harte,
Bris, R.; Holmes, S. M. J. Am. Chem. Soc. 2008, 130, 252−258.
(b) Zhang, Y. Z.; Li, D.-F.; Clerac, R.; Kalisz, M.; Mathoniere, C.;
Holmes, S. M. Angew. Chem., Int. Ed. 2010, 49, 2941−2944. (c) Siretanu,
D.; Li, D.-F.; Buisson, L.; Bassani, D. M.; Holmes, S. M.; Mathoniere, C.;
Clerac, R. Chem. - Eur. J. 2011, 17, 11704−11708. (d) Jeon, I.-R.;
Calancea, S.; Panja, A.; Pinero Cruz, D. M.; Koumousi, E. S.;
̀ ́
e, C.; Clerac, R.; Dunbar, K. R. Inorg.
́
́ ̀
E.; Mathoniere, C.; Le
́
̀
̀
́
̃
Dechambenoit, P.; Coulon, C.; Wattiaux, A.; Rosa, P.; Mathonier
̀
e,
C.; Cler
́
ac, R. Chem. Sci. 2013, 4, 2463−2470. (e) Cao, L.; Tao, J.; Gao,
Q.; Liu, T.; Xia, Z.; Li, D. Chem. Commun. 2014, 50, 1665. (f) Koumousi,
E. S.; Jeon, I.-R.; Gao, Q.; Dechambenoit, P.; Woodruff, D. N.; Merzeau,
P.; Buisson, L.; Jia, X. L.; Li, D.-F.; Volatron, F.; Mathonier
R. J. Am. Chem. Soc. 2014, 136, 15461. (g) Zhang, Y.-Z.; Ferko, P.;
Siretanu, D.; Ababei, R.; Rath, N. P.; Shaw, M. J.; Clerac, R.; Mathoniere,
C.; Holmes, S. M. J. Am. Chem. Soc. 2014, 136, 16854−16864.
̀ ́
e, C.; Clerac,
and C23) of bipyridine groups (1·2MeOH100 K: O1···C28#2
=
2.884(4) Å, #2 = 1 − x, 1 − y, 2 − z; O7···C23#3 = 2.949(4) Å, #3
= −x, 2 − y, 2 − z; see Table S2 and Figure S6 in the SI). For
complex 2,5e the bigger ethyl groups separating the squares
eliminate the intermolecular π−π interactions and the non-
classical hydrogen bonds, thus leading to the crossover behavior
and no hysteresis.
́
̀
(6) (a) Nihei, M.; Sekine, Y.; Suganami, N.; Nakazawa, K.; Nakao, A.;
Nakao, H.; Murakami, Y.; Oshio, H. J. Am. Chem. Soc. 2011, 133, 3592−
3600. (b) Mitsumoto, K.; Oshiro, E.; Nishikawa, H.; Shiga, T.;
Yamamura, Y.; Saito, K.; Oshio, H. Chem. - Eur. J. 2011, 17, 9612−9618.
(c) Nihei, M.; Okamoto, Y.; Sekine, Y.; Hoshino, N.; Shiga, T.; Liu, I. P.-
C.; Oshio, H. Angew. Chem., Int. Ed. 2012, 51, 6361−6364. (d) Hoshino,
N.; Iijima, F.; Newton, G. N.; Yoshida, N.; Shiga, T.; Nojiri, H.; Nakao,
A.; Kumai, R.; Murakami, Y.; Oshio, H. Nat. Chem. 2012, 4, 921−926.
(e) Newton, G. N.; Mitsumoto, K.; Wei, R.; Iijima, F.; Shiga, T.;
Nishikawa, H.; Oshio, H. Angew. Chem., Int. Ed. 2014, 53, 2941−2944.
(7) (a) Liu, T.; Zhang, Y.; Kanegawa, S.; Kang, S.; Sato, O. Angew.
Chem., Int. Ed. 2010, 49, 8645−8648. (b) Liu, T.; Zhang, Y.; Kanegawa,
S.; Sato, O. J. Am. Chem. Soc. 2010, 132, 8250−8251. (c) Liu, T.; Dong,
D.-P.; Kanegawa, S.; Kang, S.; Sato, O.; Shiota, Y.; Yoshizawa, K.;
Hayami, S.; Wu, S.; He, C.; Duan, C.-Y. Angew. Chem., Int. Ed. 2012, 51,
4367−4370. (d) Dong, D.-P.; Liu, T.; Kanegawa, S.; Kang, S.; Sato, O.;
He, C.; Duan, C.-Y. Angew. Chem., Int. Ed. 2012, 51, 5119−5123.
(8) (a) Mercurol, J.; Li, Y.; Pardo, E.; Risset, O.; Seuleiman, M.;
ASSOCIATED CONTENT
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S
* Supporting Information
The Supporting Information is available free of charge on the
Synthetic, spectroscopic, crystallographic, and magnetic
X-ray crystallorgraphic data in CIF format (CIF)
AUTHOR INFORMATION
Rousseliere, H.; Lescouezec, R.; Julve, M. Chem. Commun. 2010, 46,
̀
̈
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8995−8997. (b) Mondal, A.; Li, Y.; Seuleiman, M.; Julve, M.; Toupet,
Corresponding Author
L.; Buron-Le Cointe, M.; Lescouezec, R. J. Am. Chem. Soc. 2013, 135,
̈
1653−1656. (c) Mondal, A.; Chamoreau, L.-M.; Li, Y.; Journaux, Y.;
Notes
Seuleiman, M.; Lescouezec, R. Chem. - Eur. J. 2013, 19, 7682−7685.
̈
(9) Podgajny, R.; Chorazy, S.; Nitek, W.; Rams, M.; Majcher, A. M.;
The authors declare no competing financial interest.
̇
Marszałek, B.; Zukrowski, J.; Kapusta, C.; Sieklucka, B. Angew. Chem.,
Int. Ed. 2013, 52, 896−900.
ACKNOWLEDGMENTS
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(10) Wang, C.-F.; Liu, W.; Song, Y.; Zhou, X.-H.; Zuo, J.-L.; You, X.-Z.
Eur. J. Inorg. Chem. 2008, 2008, 717−727.
We thankful for support from the NNSF of China (Grants
21471063 and 21172084) and self-determined research funds of
CCNU from the colleges’ basic research and operation of MOE.
(11) Li, D.-F.; Parkin, S.; Wang, G.; Yee, G. T.; Prosvirin, A. V.;
Holmes, S. M. Inorg. Chem. 2005, 44, 4903−4905.
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