Framework Engineering by Anions and Porous Functionalities of Cu(II)/4,4‘-bpy Coordination Polymers

Noro, Shin Ichiro; Kitaura, Ryo; Kondo, Mitsuru; Kitagawa, Susumu; Ishii, Takeshi; Matsuzaka, Hiroyuki; Yamashita, Masahiro

doi:10.1021/ja0113192

Cited by 679 publications

(327 citation statements)

References 85 publications

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“…All of the 4,4-bipy molecules act asd oubly bridging ligands. The Cu-Nbond lengths are in the range of 2.004(9) Åto 2.094(10) Å,which are in agreement with those reported for copper(II)ion and 4,4-bipy complexes [11]. The copper centers are bridged by 4,4-bipy ligands to form atwo-dimensionallayers having channels.…”

supporting

confidence: 78%

Crystal structure of tetrakis(4,4′-bipyridine)copper(I) perchlorate, [Cu(C10H8N2)4][ClO4]

Qin¹,

Li²,

Guo³

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe title compound wasprepared under hydrothermalconditions. Inatypicalexperiment, 4,4¢ -bipyridine (1 mmol) in anaqueous solution (10 mL)ofNaOH (1 mmol)wasmixed with anaqueous solution (12 mL)ofCu(ClO 4 ) 2 (2 mmol) and N -benzenesulfonyl-L -glutamic acid (2 mmol). After stirring for 5min in air, triethylamine (0.5 mmol) wasadded and then the mixture wasplaced into 25 mLTeflon-lined autoclave and heated at160°Cfor 72 h. The autoclave wascooled atarate 5K/h. The titlecomplex asred prismatic crystalwascollected by filtration, washed with water, and dried in air. DiscussionThe rationaldesign and syntheses of novel coordination polymers have achieved considerableprogressinthe field of supramolecularchemistry and crystalengineering, owing to their potentialapplications for gasstorage, sensor technology, separation processes, ion exchange, luminescence, magnetism, and catalysis, aswell as due to their intriguing variety of architectures and topologies [1][2][3][4][5].Particularly classicall igands are represented by molecules containing two 4-pyridyldonor units interconnected by chains or groups of different class, such aspyrazine, 4,4¢ -bipyridine, and 4,4¢ -azobispyridine. Numerous polymeric transition metalcomplexes with 4,4¢ -bipy have been synthesized and structurally characterized to date [6][7][8]. 4,4¢ -bipyridine is anidealconnector between the transition metalatoms for the propagation of coordination networks due to it hastwo potentialbinding sites [9-10]. During our investigation of the assembly of metalions and mixed ligands (4,4¢ -bipyridine and N -benzenesulfonyl-L -glutamic acid), we did not obtain the expected compound. Insteadthe red prismatic crystals of the title complex grew from the solution. Int he title crystals tructure, six Cu(II)c enters are separated by 4,4-bipy spacerst og ive alarge rhombus arrangement, where each metaladopts atetrahedralenvironment and is bound to four 4,4-bipy ligands. All of the 4,4-bipy molecules act asd oubly bridging ligands. The Cu-Nbond lengths are in the range of 2.004(9) Åto 2.094(10) Å,which are in agreement with those reported for copper(II)ion and 4,4-bipy complexes [11]. The copper centers are bridged by 4,4-bipy ligands to form atwo-dimensionallayers having channels. Unlike many other solids with interpenetrating networks, the extent of interpenetrating in the title structure does not fill all the available voids but leaves asignificant portion of them which are occupied by disordered ClO 4 -anion. This type of frameworkinterpenetration hasbeen observed for four interpenetration diamond-like frameworkswith the PF 6 anions inside [12]. The N -benzenesulfonyl-L -glutamic acid ligand obviously acts asreducing agent in the reduction of Cu(II)/Cu(I). The mechanistic details of the redox process are not completely clear. Some similarphenomenons have been observed previously [13][14]

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supporting

confidence: 78%

Crystal structure of tetrakis(4,4′-bipyridine)copper(I) perchlorate, [Cu(C10H8N2)4][ClO4]

Qin¹,

Li²,

Guo³

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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“…We succeeded in the synthesis of the three-dimensional MOF, {[Cu 2 (PF 6 )(NO 3 )(4,4′-bpy) 4 ]•2PF 6 }, in which the PF 6 − and NO 3 − anions alternately bridged the Cu(II) axial sites of adjacent two-dimensional layers with Cu-F and Cu-O distances of 2.676(4) and 2.320(5) Å, respectively (Figure 7a). 25 In fact, this MOF was stable after the removal of guest molecules and the desolvated form showed a type I adsorption isotherm for N 2 at 77 K with a Brunauer-Emmett-Teller specific surface area of 559 m 2 g − 1 , suggesting the presence of stable micropores (Figure 7b). The SiF 6 2 − pillars had an important role in the formation of favorable MOFsorbate interactions via non-coordinated F atoms, which was confirmed using modeling studies, and X-ray and neutron diffraction analysis.…”

Section: Mofs Functionalized With Inorganic Fluorinated Anionsmentioning

confidence: 99%

“…AF 6 2 − anions (A = Si, Ge, Sn and Ti) can be used as bridging ligands for MOFs due to their high density of negative charge on fluorine atoms. [18][19][20][21][22][23][24][25][26][27]29,50 There are many AF 6 2 − -bridged MOFs, Fluorine-functionalized MOFs/PCPs S Noro and T Nakamura primitive cubic structure constructed from two-dimensional [M(4,4′-bpy) 2 ] n sheets and inorganic SiF 6 2 − pillars. 18,19 The Cu(II) compound, [Cu(SiF 6 )(4,4′-bpy) 2 ] (SIFSIX-1-Cu), was shown to have permanent pores and exhibit a high uptake of CH 4 (6.5 mmol g − 1 at 298 K and 36 atm) and selective CO 2 uptake over CH 4 (10.5 (IAST CO 2 /CH 4 (50:50) selectivity) at 298 K and 1 atm), and selective C 2 H 2 uptake over C 2 H 4 (8.37 (IAST C 2 H 2 /C 2 H 4 (50:50) selectivity) at 298 K and 1 atm).…”

Section: Mofs Functionalized With Inorganic Fluorinated Anionsmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal-organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics. NPG Asia Materials (2017) 9, e433; doi:10.1038/am.2017.165; published online 29 September 2017 INTRODUCTIONDuring the last two decades, metal-organic frameworks (MOFs)/ porous coordination polymers (PCPs) composed of metal ions and organic bridging ligands as main building units and, in some cases, inorganic ligands, have been investigated extensively because of their versatile structural diversity, high structural controllability (pore size, shape, dimension, flexibility and surface environment), high crystallinity, and their potential porous properties/functionalities in a variety of research fields such as storage and separation, catalysis, drug delivery and sensing ability. 1-3 The porous properties of MOFs/PCPs can be finely tailored by not only chemical modification of organic ligands and judicious choice of components but also a variety of techniques such as solid solution formation, defect engineering, core-shell structure, crystal morphology and size control, and so on. For example, the appropriate combination of organic bridging ligands provided the Zn(II) MOF, [Zn 4 O(bte) 4/3 (bpdc)] (bte = 4,4′,4′′-[benzene-1,3,5-triyl-tris (ethyne-2,1-diyl)]tribenzoate, bpdc = biphenyl-4,4′-dicarboxylate), with ultra-high Brunauer-Emmett-Teller and Langmuir specific surface areas close to 6000 and 10 000 m 2 g − 1 , respectively. 4 Unlike porous inorganic zeolites and porous carbon materials, MOFs often give flexible structures. As coordination bonds, hydrogen bonds and van der Waals interactions that are used to assemble each component are weaker (bonding energies are 10~200 kJ mol − 1 ) than covalent and ionic bonds (200~1000 kJ mol − 1 ), reversible rotation, bending and breaking of these weaker bonds easily occurs, resulting in structural changes. One representative of flexible MOFs is [Cr(OH)(1,4-bdc)] (MIL-53(Cr), 1,4-bdc = 1,4-benzenedicarboxylate), in which local reorientation of the coordination bond triggered by guest adsorption/ desorption induced the structural transformation between narrow pore and large pore forms. 5 In addition, many MOFs show high crystallinity as with porous inorganic zeolites, which is advantageous for understanding deeply the structure-property relationship using single-crystal and powder X-ray diffraction techniques. For example, the unprecedented highly selective CO sorption from a CO/N 2 mixture, which is

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“…Using this characteristic, capture of weak Lewisbase PF 6 -anions has been achieved. 3,5 The unusual linear Cu-F-Cu bridge with orthogonal Jahn-Teller axes is therefore attributed to the contribution of a directionless electrostatic interaction between the Cu1 and F13 ions.…”

mentioning

confidence: 99%

Orthogonality of Jahn–Teller axes in a dinuclear Cu(ii) complex bridged by one F− anion

2010

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The dinuclear Cu(II) complex bridged by a single F -anion has orthogonal Jahn-Teller axes, which induce a ferromagnetic interaction between the intramolecular Cu(II) ions.The Cu(II) ion, which has a d 9 configuration, shows a Jahn-Teller distortion that enables the addition of interesting properties such as flexibility, 1 unsaturated coordination sites, 2 unprecedented bonding modes derived from electrostatic interactions, 3,4 and polar structures, 5 to metal complexes. For example, we have recently developed a synthetic method to introduce polar structures in coordination polymers using Cu(II) ions and weak Lewis-base PF 6 -anions. The resulting polar coordination polymers showed highly selective CO 2 adsorption properties with structural transformations. 5 In this paper, we report the synthesis, crystal structure, and physical properties of the dinuclear Cu(II) complex [Cu 2 F(BF 4 ) 3 (4-phpy) 7 ] (1, 4-phpy = 4-phenylpyridine) bridged by a single F -anion, in which a Jahn-Teller distortion contributes to the formation of a unique structure and properties.Blue crystals of 1 were obtained by slow diffusion of a methanol solution containing Cu(BF 4 ) 2 ·xH 2 O and a toluene solution containing 4-phpy in an H-type glass cell. 6 The bridged F -anion originates from the hydrolysis of one equivalent of the BF 4 -anion, 7 a well-documented phenomenon that has also been utilized to yield coordination compounds with bridged F -anions. 8,9 Fig. 1 ORTEP drawing of 1 (thermal ellipsoids drawn at 50% probability).The hydrogen atoms are omitted for clarity.

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Framework Engineering by Anions and Porous Functionalities of Cu(II)/4,4‘-bpy Coordination Polymers

Cited by 679 publications

References 85 publications

Crystal structure of tetrakis(4,4′-bipyridine)copper(I) perchlorate, [Cu(C10H8N2)4][ClO4]

Crystal structure of tetrakis(4,4′-bipyridine)copper(I) perchlorate, [Cu(C10H8N2)4][ClO4]

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Orthogonality of Jahn–Teller axes in a dinuclear Cu(ii) complex bridged by one F− anion

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