TY - JOUR
T1 - Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions
AU - Ohtani, Ryo
AU - Yanagisawa, Junichi
AU - Matsunari, Hiromu
AU - Ohba, Masaaki
AU - Lindoy, Leonard F.
AU - Hayami, Shinya
PY - 2019/10/7
Y1 - 2019/10/7
N2 - Two-dimensional Hofmann-type coordination polymers of type Mn(H2O)2[Pd(CN)4]·xH2O (1·xH2O; x = 0, 1, and 4), Mn(H2O)(MeOH)[Pd(CN)4]·2MeOH (2·2MeOH), and Mn(MeOH)2[Pd(CN)4]·MeOH (3·MeOH) have been synthesized. The homosolvent-bound 1·4H2O, 1·H2O, and 3·MeOH polymers consist of undulating layer structures, whereas the structure of heterosolvent-bound 2·2MeOH consists of "Janus-like" flat layers in which water-bound and MeOH-bound-sides are present. 1·4H2O and 1·H2O exhibited anisotropic two-dimensional thermal expansions involving structural transformations of the undulating layers; one layer axis expands while the other contracts. 2·2MeOH exhibits anisotropic thermal expansion in which the flat layers shift sideways as the temperature is increased, with colossal interlayer expansion occurring (αc = +200 MK-1 over 140-180 K, αc = +165 MK-1 over 200-280 K). 3·MeOH also showed colossal interlayer expansion (αc = +216 MK-1) together with expansion of the undulating layers.
AB - Two-dimensional Hofmann-type coordination polymers of type Mn(H2O)2[Pd(CN)4]·xH2O (1·xH2O; x = 0, 1, and 4), Mn(H2O)(MeOH)[Pd(CN)4]·2MeOH (2·2MeOH), and Mn(MeOH)2[Pd(CN)4]·MeOH (3·MeOH) have been synthesized. The homosolvent-bound 1·4H2O, 1·H2O, and 3·MeOH polymers consist of undulating layer structures, whereas the structure of heterosolvent-bound 2·2MeOH consists of "Janus-like" flat layers in which water-bound and MeOH-bound-sides are present. 1·4H2O and 1·H2O exhibited anisotropic two-dimensional thermal expansions involving structural transformations of the undulating layers; one layer axis expands while the other contracts. 2·2MeOH exhibits anisotropic thermal expansion in which the flat layers shift sideways as the temperature is increased, with colossal interlayer expansion occurring (αc = +200 MK-1 over 140-180 K, αc = +165 MK-1 over 200-280 K). 3·MeOH also showed colossal interlayer expansion (αc = +216 MK-1) together with expansion of the undulating layers.
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U2 - 10.1021/acs.inorgchem.9b01660
DO - 10.1021/acs.inorgchem.9b01660
M3 - Article
C2 - 31539234
AN - SCOPUS:85072934364
VL - 58
SP - 12739
EP - 12747
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 19
ER -