ja4076056_si_002.cif (52.12 kB)
Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru2II,II]/[Rh2II,II] Dimers
dataset
posted on 2013-12-11, 00:00 authored by Wataru Kosaka, Kayo Yamagishi, Akihiro Hori, Hiroshi Sato, Ryotaro Matsuda, Susumu Kitagawa, Masaki Takata, Hitoshi MiyasakaThe design of porous materials that
undergo selective adsorption
of a specific molecule is a critical issue in research on porous coordination
polymers or metal–organic frameworks. For the purpose of the
selective capture of molecules possessing an electron-acceptor character
such as nitric oxide (NO), one-dimensional chain compounds possessing
a high donor character have been synthesized using 4-chloroanisate-bridged
paddlewheel-type dimetal(II, II) complexes with M = Ru and Rh and
phenazine (phz) as the chain linker: [M2(4-Cl-2-OMePhCO2)4(phz)]·n(CH2Cl2) (M = Ru, 1; Rh, 2). These
compounds are isostructural and are composed of chains with a [−{M2}–phz−] repeating unit and CH2Cl2 occupying the void space between the chains. Compounds 1 and 2 change to a new phase (1-dry and 2-dry) upon evacuating the crystallization solvent
(CH2Cl2) and almost lose their pores in the
drying process: no void space in 1-dry and 31.8 Å3, corresponding to 2.9% of the cell volume, in 2-dry. Nevertheless, the compounds show a unique gas accommodation ability.
Accompanied by a structural transformation (i.e., the first gate-opening)
at low pressures of <10 kPa, both compounds show a typical physisorption
isotherm for O2 (90 K) and CO2 (195 K), with
the adsorption amount of ca. 2–4 gas molecules per [M2] unit. In addition, the adsorption isotherm for NO (121 K) involves
the first gate-opening followed by a second gate-opening anomaly at
NO pressures of ≈52 kPa for 1-dry and ≈21
kPa for 2-dry. At the first gate-opening, the absorbed
amount of NO is ca. 4 molecules per [M2] unit, and then
it reaches 8.4 and 6.3 for 1-dry and 2-dry, respectively, at 95 kPa. Only the isotherm for NO exhibits hysteresis
in the desorption process, and some of the NO molecules are trapped
in pores even after evacuating at 121 K, although it recovers to the
original dried sample on heating to room temperature. The adsorbed
NO molecules accrue a significant electron donation from the host
framework even in the [Rh2] derivative, indicating that
such simple porous compounds with electron-donor characteristics are
useful for the selective adsorption of NO.