Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions

Ryo Ohtani, Junichi Yanagisawa, Hiromu Matsunari, Masaaki Ohba, Leonard F. Lindoy, Shinya Hayami

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)12739-12747
Number of pages9
JournalInorganic chemistry
Volume58
Issue number19
DOIs
Publication statusPublished - Oct 7 2019

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Thermal expansion
thermal expansion
interlayers
flat layers
Polymers
expansion
Janus
coordination polymers
Water
shift
polymers
water
Temperature
temperature

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions. / Ohtani, Ryo; Yanagisawa, Junichi; Matsunari, Hiromu; Ohba, Masaaki; Lindoy, Leonard F.; Hayami, Shinya.

In: Inorganic chemistry, Vol. 58, No. 19, 07.10.2019, p. 12739-12747.

Research output: Contribution to journalArticle

Ohtani, Ryo ; Yanagisawa, Junichi ; Matsunari, Hiromu ; Ohba, Masaaki ; Lindoy, Leonard F. ; Hayami, Shinya. / Homo- and Heterosolvent Modifications of Hofmann-Type Flexible Two-Dimensional Layers for Colossal Interlayer Thermal Expansions. In: Inorganic chemistry. 2019 ; Vol. 58, No. 19. pp. 12739-12747.
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abstract = "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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