TY - JOUR
T1 - Dynamic transformation and reversible guest encapsulations of pseudopolymorphs of a fully fluorinated β-diketonate Pd(II) complex
AU - Nakajima, Kyosuke
AU - Hori, Akiko
PY - 2014/7/2
Y1 - 2014/7/2
N2 - Two types of pseudopolymorphs, 1·(2)3 and 1·(2)2, were obtained from Pd(II) complex (1) with mesitylene (2), and the quantitative transformation into 1·(2)2 from 1·(2)3 was observed over 6 h after shaking for approximately 10 s. The transformation was observed in both a mesitylene-rich solution and under powder conditions. The guest release processes of 1·(2)3 and 1·(2)2 occurred in hexane to yield 1, and the guest insertion processes occurred in 2 to reproduce 1·(2)3 and 1·(2)2, whereas each crystal was constructed from the discrete molecules of each type. These crystals also selectively and repeatedly encapsulated three benzenes or one toluene in the uniform cavities of 1·(2)3 and 1·(2)2. In contrast, the corresponding nonfluorinated derivative, [Pd(dbm)2] (dbm = dibenzoylmetanide), shows no guest encapsulation phenomena, indicating that the remarkable guest encapsulations are induced by fluorine substitutions. The dynamic crystal transformation and the reversible guest encapsulations of the two pseudopolymorphs were investigated by X-ray crystallographic and thermogravimetric studies for both single crystals and powder species.
AB - Two types of pseudopolymorphs, 1·(2)3 and 1·(2)2, were obtained from Pd(II) complex (1) with mesitylene (2), and the quantitative transformation into 1·(2)2 from 1·(2)3 was observed over 6 h after shaking for approximately 10 s. The transformation was observed in both a mesitylene-rich solution and under powder conditions. The guest release processes of 1·(2)3 and 1·(2)2 occurred in hexane to yield 1, and the guest insertion processes occurred in 2 to reproduce 1·(2)3 and 1·(2)2, whereas each crystal was constructed from the discrete molecules of each type. These crystals also selectively and repeatedly encapsulated three benzenes or one toluene in the uniform cavities of 1·(2)3 and 1·(2)2. In contrast, the corresponding nonfluorinated derivative, [Pd(dbm)2] (dbm = dibenzoylmetanide), shows no guest encapsulation phenomena, indicating that the remarkable guest encapsulations are induced by fluorine substitutions. The dynamic crystal transformation and the reversible guest encapsulations of the two pseudopolymorphs were investigated by X-ray crystallographic and thermogravimetric studies for both single crystals and powder species.
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U2 - 10.1021/cg500222y
DO - 10.1021/cg500222y
M3 - Article
AN - SCOPUS:84903741002
VL - 14
SP - 3169
EP - 3173
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 7
ER -