title: Rational Synthesis and Investigation of Porous Metal-Organic Framework Materials from a Preorganized Heterometallic Carboxylate Building Block.
abstract: The tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (1, where piv-= pivalate and py = pyridine) has been successfully employed as a presynthesized node for the construction of four porous metal-organic frameworks (MOFs) [Li2Zn2(R-bdc)3(bpy)]·solv (2-R, R-bdc2-; R = H, Br, NH2, NO2) by reaction with 4,4'-bipyridine (bpy) and terephthalate anionic linkers. The [Li2Zn2] node is retained in the products, representing a rare example of the rational step-by-step design of isoreticular MOFs based on complex heterometallic building units. The permanent porosity of the activated frameworks was confirmed by gas adsorption isotherm measurements (N2, CO2, CH4). Three compounds, 2-H, 2-Br, and 2-NH2(but not 2-NO2), feature extensive hysteresis between the adsorption and desorption curves in the N2isotherms at low pressures. The substituents R decorate the inner surface and also control the aperture of the channels, the volume of the micropores, and the overall surface area, thus affecting both the gas uptake and adsorption selectivity. The highest CO2absorption at ambient conditions (105 cm3·g-1or 21 wt % at 273 K and 1 bar for 2-NO2) is above the average values for microporous MOFs. The photoluminescent properties of the prototypic 2-H as well as the corresponding host-guest compounds with various aromatic molecules (benzene, toluene, anisole, and nitrobenzene) were systematically investigated. We discovered a rather complex pattern in the emission response of this material depending on the wavelength of excitation as well as the nature of the guest molecules. On the basis of the crystal structure of 2-H, a mechanism for these luminescent properties is proposed and discussed.
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.
authors.forename: Aleksandr A
authors.initials: AA
authors.lastname: Sapianik
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, RAS , 31 Leninsky Avenue, 119991 Moscow, Russia.
authors.forename: Ekaterina N
authors.identifier: http://orcid.org/0000-0002-6456-9584
authors.initials: EN
authors.lastname: Zorina-Tikhonova
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, RAS , 31 Leninsky Avenue, 119991 Moscow, Russia.
authors.forename: Mikhail A
authors.initials: MA
authors.lastname: Kiskin
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.|Novosibirsk State University , 2 Pirogova Street, 630090 Novosibirsk, Russia.
authors.forename: Denis G
authors.initials: DG
authors.lastname: Samsonenko
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.|Novosibirsk State University , 2 Pirogova Street, 630090 Novosibirsk, Russia.
authors.forename: Konstantin A
authors.initials: KA
authors.lastname: Kovalenko
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, RAS , 31 Leninsky Avenue, 119991 Moscow, Russia.
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Sidorov
authors.affiliation: N. S. Kurnakov Institute of General and Inorganic Chemistry, RAS , 31 Leninsky Avenue, 119991 Moscow, Russia.
authors.forename: Igor L
authors.initials: IL
authors.lastname: Eremenko
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.|Novosibirsk State University , 2 Pirogova Street, 630090 Novosibirsk, Russia.
authors.forename: Danil N
authors.identifier: http://orcid.org/0000-0001-8779-0612
authors.initials: DN
authors.lastname: Dybtsev
authors.affiliation: School of Chemistry, University of Nottingham , Nottingham NG7 2RD, U.K.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: School of Chemistry, University of Nottingham , Nottingham NG7 2RD, U.K.
authors.forename: Stephen P
authors.initials: SP
authors.lastname: Argent
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.|School of Chemistry, University of Manchester , Manchester M13 9PL, U.K.
authors.forename: Martin
authors.initials: M
authors.lastname: Schröder
authors.affiliation: Nikolaev Institute of Inorganic Chemistry, SB RAS , 3 Akad. Lavrentiev Avenue, 630090 Novosibirsk, Russia.|Novosibirsk State University , 2 Pirogova Street, 630090 Novosibirsk, Russia.
authors.forename: Vladimir P
authors.initials: VP
authors.lastname: Fedin