Atsushi Kobayashi, Yui Suzuki, Tadashi Ohba, Tomohiro Ogawa, Takeshi Matsumoto, Shin-ichiro Noro, Ho-Chol Chang, Masako Kato
INORGANIC CHEMISTRY 54 (6) 2522 - 2535 0020-1669 2015/03
[Refereed][Not invited] A series of flexible porous coordination polymers (PCPs) RE-Co, composed of a Co(III)-metalloligand [Co(dcbpy)(3)](3-) (Co; H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and lanthanide cations (RE3+ = La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Er3+), was systematically synthesized. X-ray crystallographic analysis revealed that the six carboxylates at the top of each coordination octahedron of Co(III)-metalloligand were commonly bound to RE3+ cations to form a rock-salt-type porous coordination framework. When RE-Co contains a smaller and heavier RE3+ cation than Nd3+, the RE-Co crystallized in the cubic Fm-3m space group, whereas the other three RE-Co with larger RE3+ crystallized in the lower symmetrical orthorhombic Fddd space group, owing to the asymmetric 10-coordinated bicapped square antiprism structure of the larger RE3+ cation. Powder X-ray diffraction and vapor-adsorption isotherm measurements revealed that all synthesized RE-Co PCPs show reversible amorphous-crystalline transitions, triggered by water-vapor-adsorption/desorption. This transition behavior strongly depends on the kind of RE3+; the transition of orthorhombic RE-Co was hardly observed under exposure to CH3OH vapor, but the RE-Co with smaller cations such as Gd3+ showed the transition under exposure to CH3OH vapors. Further tuning of vapor-adsorption property was examined by doping of Ru(II)-metalloligands, [Ru(dcbpy)(3)](4-), [Ru(dcbpy)(2)Cl-2](4-), [Ru(dcbpy)(tpy)Cl](-), and [Ru(dcbpy)(dctpy)](3-) (abbreviated as RuA, RuB, RuC, and RuD, respectively; tpy = 2,2':6',2?-terpyridine, H2dctpy = 4,4"-dicarboxy-2,2':6',2"-terpyridine), into the Co(III)-metalloligand site of Gd-Co to form the Ru(II)-doped PCP RuX@Gd-Co (X = A, B, C, or D). Three Ru(II)-metalloligands, RuA, RuB, and RuD dopants, were found to be uniformly incorporated into the Gd-Co framework by replacing the original Co(III)-metalloligand, whereas the doping of RuC failed probably because of the less number of coordination sites. In addition, we found that the RuA doping into the Gd-Co PCP had a large effect on vapor-adsorption due to the electrostatic interaction originating from the negatively charged RuA sites in the framework and the charge-compensating Li+ cations in the porous channel.