Network Dimensionality of Selected Uranyl(VI) Coordination Polymers

Subscriber access provided by The Library | University of Bath

Article

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers and Octopus like Uranium(IV) Clusters. Ralph A. Zehnder, James M. Boncella, Justin N. Cross, Stosh A Kozimor, Marisa Jennifer Monreal, Henry S. La Pierre, Brian L. Scott, Aaron Maurice Tondreau, and Matthias Zeller Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01165 • Publication Date (Web): 31 Aug 2017 Downloaded from http://pubs.acs.org on September 2, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers and Octopus like Uranium(IV) Clusters.

Ralph A. Zehnder,*a James M. Boncella,b Justin N. Cross,b Stosh A. Kozimor,b Marisa J. Monreal, b Henry S. La Pierre,b,c Brian L. Scott,b Aaron M. Tondreau,b and Matthias Zellerd a Department of Chemistry and Biochemistry, Angelo State University, San Angelo, TX 76909, b Los Alamos National Laboratory, Los Alamos, NM 87545, cDepartment of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400, and dDepartment of Chemistry, Purdue University, West Lafayette, IN 47907 ABSTRACT Using slow diffusion methods at room temperature, five uranium coordination polymers were obtained, which either employ glutarate (Glut), terephthalate (TP), or 2-aminoterephthalate (TPNH2) as bridging systems. Four of these networks are based on the uranyl(VI)-unit, UO22+, and one formed through the integration of tetravalent uranium as the coordinating metal center. [[UO2](TP)(H2O)2]·2THF (1) arranges as intermeshed 1-dimensional (1D) infinite linear chains, locked into a 3-dimensional (3D) network through hydrogen bonds with a uninodal 4coordinated uom topology. [[UO2](TPNH2)(H2O)2]•2H2O (2) assembles as intermeshed 2dimensional (2D) layers, also stabilized as a 3D-network through hydrogen bonding with a 2nodal 4-coordinated pts network topology. Na2[[UO2]2(TP)3]•9H2O (3) forms parallel layers that are stacked in an AB pattern. Layers possess the uninodal 3-coordinate honeycomb (hcb) motif. Na2[[UO2]2(Glut)3]•8H2O (4) assembles as a 3D-coordination network with a uninodal 3-c srs (SrSi2) topology. The fifth compound contains uranium(IV) and the glutarate entity; U6(NO3)4(Glut)4(O)4(OH)4(H2O)6·12H2O (5). The long-range structure of 5 adopts a 3D-open framework, as it includes the flexible glutarate linker, in which U6O8 SBUs assemble as U6O38 superclusters. These clusters are interlinked by the glutarate spacers resulting in a body centered cubic (bcu) topology.

*Dr. Ralph Zehnder Assistant Professor of Chemistry Department of Chemistry & Biochemistry Angelo State University ASU Station #10892, CAV 204B San Angelo, TX 76909-0892 Phone: +1-325-486-6662, Fax: (325) 942-2184 [email protected] www.angelo.edu/content/profiles/975-ralph-zehnder

ACS Paragon Plus Environment

1


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 74

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers and Octopus like Uranium(IV) Clusters. Ralph A. Zehnder,*a James M. Boncella,b Justin N. Cross,b Stosh A. Kozimor,b Marisa J. Monreal, b Henry S. La Pierre,b,c Brian L. Scott,b Aaron M. Tondreau,b and Matthias Zellerd a

Department of Chemistry and Biochemistry, Angelo State University, San Angelo, TX 76909, b

Los Alamos National Laboratory, Los Alamos, NM 87545, cDepartment of Chemistry and

Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332-0400, and dDepartment of Chemistry, Purdue University, West Lafayette, IN 47907

ABSTRACT

Using slow diffusion methods at room temperature, five uranium coordination polymers were obtained, which either employ glutarate (Glut), terephthalate (TP), or 2-aminoterephthalate (TPNH2) as bridging systems. Four of these networks are based on the uranyl(VI)-unit, UO22+, and one formed through the integration of tetravalent uranium as the coordinating metal center. [[UO2](TP)(H2O)2]·2THF (1) arranges as intermeshed 1-dimensional (1D) infinite linear chains, locked into a 3-dimensional (3D) network through hydrogen bonds with a uninodal 4coordinated uom topology. [[UO2](TPNH2)(H2O)2]•2H2O (2) assembles as intermeshed 2-


2

Page 3 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


dimensional (2D) layers, also stabilized as a 3D-network through hydrogen bonding with a 2nodal 4-coordinated pts network topology. Na2[[UO2]2(TP)3]•9H2O (3) forms parallel layers that are stacked in an AB pattern. Layers possess the uninodal 3-coordinate honeycomb (hcb) motif. Na2[[UO2]2(Glut)3]•8H2O (4) assembles as a 3D-coordination network with a uninodal 3-c srs (SrSi2) topology. The fifth compound contains uranium(IV) and the glutarate entity; U6(NO3)4(Glut)4(O)4(OH)4(H2O)6·12H2O (5). The long-range structure of 5 adopts a 3D-open framework, as it includes the flexible glutarate linker, in which U6O8 SBUs assemble as U6O38 superclusters. These clusters are interlinked by the glutarate spacers resulting in a body centered cubic (bcu) topology.

INTRODUCTION Recent advances in synthetic inorganic chemistry have revealed that metal organic frameworks (MOFs) have potential to solve some technical problems associated with f-elements. Over the last two decades, MOFs have received the attention of prominent researchers,1-7 owing to their unique properties and their potential applications in optical,8, electronic12,

13

9

magnetic,10,

11

and

systems. These properties set MOFs apart from conventional materials and

enabled them to emerge as a focus point across the inorganic chemistry community. For example, MOFs consist of three-dimensional (3D), or two-dimensional (2D) porous networks with the capacity to accommodate atoms, ions, or small molecules within their cavities. The ability to maintain their structural integrity upon removal of guest entities makes them highly suitable for catalysis,14-16 sensing,2, 17-20 drug delivery,21, 22 gas filtration/separation,3, 23-25 and gas storage.26-30 Within the last couple of years this research topic has exploded with rapid discovery


3


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 74

and advancement, including the design of light harvesting materials,31 micro-robotics,32,

33

photon activation,34, 35 proton conducting materials,7, 36 and super acidic systems.37 Our interest in f-element MOFs is part of a larger movement focused on using lanthanide and actinide MOFs to solve technical challenges in f-element chemistry.38-44, 45-58 In part this stems from unique f-element properties, i.e. the larger ionic radii, which provide access to unique coordination networks with increased metal coordination numbers. The local metal geometry propagates into novel topologies, not accessible with the smaller transition metal ions. Fundamentally, f-element MOFs have potential to reveal insight into actinide and lanthanide coordination chemistry. Moreover, these extended frameworks may offer potential alternative processing methods to vitrification and mineralization techniques used in long-term storage of spent nuclear fuels.59-64 Coordination polymers based on the uranyl(VI)-unit have connected actinide and MOF -research for quite some time and they exhibit rather unique structural behaviors.60, 65-68 While the relatively large ionic radius of the U6+-cation would otherwise offer quite large coordination numbers with a variety of topologies and high connectivities, the uranium(VI)-ion is mostly found to be complexed between two oxygen atoms, forming the highly stable and rigid [UO2]2+-entity. The axial arrangement of the [O=U=O]2+-unit restricts the coordination sites that can be occupied practically to the equatorial plane. This reduces the number of organic entities that can dock to uranyl sites. That in return makes it increasingly challenging to create multidimensional networks.69, 70 The use of organic linkers with various functional groups for the chelation of uranyl and other actinyl -sites may have significance in nuclear fuel reprocessing,71 or the creation of detoxification agents.72,

73

Last year Bai et al.

presented the first uranyl-MOF with anion exchange properties.56


4

Page 5 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Reported here is our attempt to expand synthetic methodologies that we developed for rare earth elements74, 75 to the 5f-elements. This involved using slow diffusion methods at room temperature and generated five uranium solids. These coordination polymers integrate glutarate (Glut), terephthalate (TP), or 2-aminoterephthalate (TPNH2) entities as spacer systems between uranium ions. In all cases, metal reagents involved UO22+ starting materials. Generally, this resulted in isolation of UO22+ containing products. However, in one case, which involved glutarate, a uranium(IV) product was obtained. This result was rather surprising as no attempt was made to exclude air and moisture during the synthetic procedure. Consider that the reduction potential of UO22+ to U4+ in aqueous media is generally quite negative (near -1 eV) and that the glutarate linker is not a strong reducing agent.

EXPERIMENTAL SECTION General Remarks. Chemicals used as starting materials were purchased from Acros Organics (2-nitroterephthalic acid), Sigma Aldrich (terephthalic acid, THF, uranyl nitrate hexahydrate), Alfa Aesar (2aminoterephthalic acid, glutaric acid) and Calbiochem (OmniPur Ethanol 200 proof), and were used without further purification. Caution: Uranyl nitrate is toxic and a weak alpha emitter in conjunction with beta emissions due to daughter products, and therefore a radiological hazard. Thus, standard ppe for the handling of alpha and beta emitters is crucial.


5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 74

Synthesis and Characterization. Synthesis of uranyl terephthalate di-hydrate with two interstitial THF molecules, [[UO2](TP)(H2O)2]·2THF (1): A 2 mL scintillation vial, 3/4 filled with DI-water, was lowered into a 15 mL Falcon PPE conical tube. A solution of Na2Glut + Na2TP (molar ratio 2:1) (100 and 50 mmol/L) in a 1:1:1 mixture of H2O/THF/EtOH was filled into the 15 mL conical tube outside of the 2 mL vial (~ 2.7 mL, 0.27 and 0.14 mmol). A small amount (~ 0.5 mL) of [UO2(NO3)2]·6H2O dissolved in DIwater (600 mmol/L, 0.3 mmol) was placed at the bottom of the 2 mL vial using a syringe and needle. The water on top served as a buffer zone to make the reactants diffuse at a slow rate. Enough water was added for the two solutions to be in contact with each other. The conical tube was then capped while the vial inside remained uncapped. Within 12 months single crystals of 1 had grown in form of thin yellow rods. Anal. calcd. for (C16H24O10U) (1) C, 31.28%; H, 3.94%. Found C, 14.38%; H, 2.24%; N, 1.90%. After adjustment for solvent loss (THF), and accounting for [UO2(NO3)2]·6H2O impurities as part of the obtained product mixture, based on 1.90% N found, anal. calcd.: C, 13.48%; H, 1.95%. FT-IR: 3010 (br), 2970 (m), 2950 (m), 2360 (m), 2320 (m), 1740 (vs), 1510 (m), 1370 (vs), 1280 (w), 1230 (s), 1220 (vs), 1090 (w), 1010 (w), 926 (s), 879 (m), 843 (s), 741 (m), 667 (w). Yield: 27.1 mg (0.0441 mmol), 31.5%.

Synthesis of uranyl 2-aminoterephthalate di-hydrate with two interstitial H2O molecules [[UO2](TPNH2)(H2O)2]·2H2O (2): The reaction of [UO2(NO3)2]·6H2O in aqueous solution with solutions of Na2Glut/Na2TPNH2 in 1:1:1 mixture of H2O/THF/EtOH resulted in the growth of single crystals in form of yellow


6

Page 7 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


blocks. A 2 mL scintillation vial 3/4 filled with water was lowered into a 15 mL Falcon PPE conical tube. A solution of Na2Glut + Na2TPNH2 (molar ratio 2:1) (60 and 30 mmol/L) in H2O/THF/EtOH (ratio 1:1:1) was filled into the 15 mL conical tube outside of the 2 mL vial (~ 2.7 mL, 0.16 and 0.08 mmol). A small amount (~ 0.5 mL) of [UO2(NO3)2]·6H2O dissolved in DIwater (600 mmol/L, 0.3 mmol) was placed at the bottom of the 2 mL vial using a syringe and needle. The water on top served as a buffer zone to make the reactants diffuse at a slow rate. Enough water was added for the two solutions to be in contact with each other. The conical tube was then capped while the vial inside remained uncapped. Within 12 months large intensive yellow crystalline conglomerates of blocks had formed, which were washed with and suspended in a 1:1 THF/EtOH mixture. Anal. calcd. for (C8H13NO10U) (2) C, 18.43%; H, 2.514%; N, 2.69%. Found C, 13.89%; H, 1.90%; N, 4.07%. After accounting for UO2(NO3)2·6H2O impurities as part of the obtained product mixture, based on excess N found, anal. calcd.: C, 11.26%; H, 2.47%; N, 4.07%. FT-IR: 3330 (br), 3220 (vs), 2900 (w), 2230 (w), 2030 (w), 1630 (s), 1590 (m), 1500 (s), 1410 (s), 1270 (s), 1140 (m), 1030 (m), 926 (s), 847 (m), 802 (w), 762 (w), 746 (m), 611 (w), 573 (m), 552 (w), 532 (m). Yield: 35.9 mg (0.0689 mmol), 86.1%.

Synthesis of sodium uranyl terephthalate nona-hydrate Na2[[UO2]2(TP)3]·9H2O (3): A 2 mL scintillation vial, completely filled with a solution of Na2TP (120 mmol/L, 0.24 mmol) in H2O, was turned upside down and lowered into a 15 mL Falcon PPE conical tube whose bottom part was filled with enough DI-H2O so that the vial opening was completely immersed in the water. Then, another 2mL scintillation vial, nearly filled with water, was lowered into the 15 mL conical tube resting atop of the first 2 mL vial, so that the two vial openings point into


7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 74

opposite directions. DI-H2O was added to the Falcon tube until the water level was even with the upper rim of the top 2 mL vial. A small amount (~ 0.5 mL) of a [UO2(NO3)2]·6H2O (83 mmol/L, 0.04 mmol) solution was placed at the bottom of the upper 2 mL vial using a syringe and needle. The water between the two vial openings served as a buffer zone to make the reactants diffuse at a slow rate. Enough water was added for the two solutions to be in contact with each other. The conical tube was then capped while the vials inside remained uncapped. Within three weeks single crystals had grown in form of small yellow rectangular blocks. Anal. calcd. for Na2U2C24O25H30 (3) C, 23.24%; H, 2.44%. Found C, 24.32%; H, 2.34%. FTIR: 3010 (w), 2970 (w), 2360 (w), 2320 (w), 1740 (s), 1530 (m), 1510 (m), 1370 (s), 1220 (s), 920 (m), 881 (w), 843 (s), 742 (m), 667 (w), 536 (s). Yield: 13.1 mg (0.00111 mmol), 5.6%.

Synthesis of disodium uranyl glutarate octa-hydrate Na2[[UO2]2(Glut)3]·8H2O (4): The reaction of [UO2(NO3)2]·6H2O in aqueous solution with Na2Glut/Na2TPNO2, also in aqueous solution, resulted in the growth of single crystals in form of large yellow cubes: A 2 mL scintillation vial, completely filled with a solution of Na2Glut (170 mmol/L, 0.34 mmol) in H2O, was turned upside down and lowered into a 15 mL Falcon PPE conical tube whose bottom part was filled with enough DI-H2O so that the vial opening was completely immersed in the water. Then, another 2mL scintillation vial, nearly filled with water, was lowered into the 15 mL conical tube resting atop of the first 2 mL vial, so that the two vial openings point into opposite directions. DI-H2O was added to the Falcon tube until the water level was even with the upper rim of the top 2 mL vial. A small amount (~ 0.5 mL) of a [UO2(NO3)2]·6H2O (83 mmol/L, 0.04 mmol) solution was placed at the bottom of the upper 2 mL vial using a syringe and needle. The water between the two vial openings served as a buffer zone to make the reactants diffuse at a


8

Page 9 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


slow rate. Enough water was added for the two solutions to be in contact with each other. The conical tube was then capped while the vials inside remained uncapped. Within 2 weeks single crystals in form of large yellow cubes had grown. Anal. calcd. for Na2U2O24C15H34 (4) C, 16.08%; H, 3.06%. Found C, 11.61%; H, 2.20%; N, 2.18%. After accounting for UO2(NO3)2 impurities as part of the obtained product mixture, based on N found, anal. calcd.: C, 11.15%; H, 2.12%. FT-IR: 3520 (br), 3020 (m), 2970 (m), 2320 (s), 1740 (vs), 1630 (m), 1530 (s), 1450 (vs), 1410 (s), 1370 (vs), 1330 (s), 1300 (s), 1230 (s), 1220 (s), 1040 (m), 922 (vs), 885 (m), 827 (s), 806 (m), 748 (m), 702 (w), 667 (w), 648 (s), 600 (w), 538 (s). Yield: 28.8 mg (0.0257 mmol), 22.7%.

Synthesis of uranium(IV) glutarate oxo nitrate with 14 interstitial water molecules U6(NO3)4(Glut)4(O)4(OH)4(H2O)6·12H2O (5): A 2 mL scintillation vial 3/4 filled with water was lowered into a 15 mL Falcon PPE conical tube. A solution of Na2Glut + Na2TP (molar ratio 2:1) (100 and 50 mmol/L) in a 1:1:1 mixture of H2O/THF/EtOH was filled into the 15 mL conical tube outside of the 2 mL vial (~ 2.7 mL, 0.27 and 0.14 mmol). A small amount (~ 0.5 mL) of [UO2(NO3)2]·6H2O dissolved in DI-water (600 mmol/L, 0.3 mmol) was placed at the bottom of the 2 mL vial using a syringe and needle. The water on top served as a buffer zone to make the reactants diffuse at a slow rate. Enough water was added for the two solutions to be in contact with each other. The conical tube was then


9


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 74

capped while the vial inside remained uncapped. Within 12 months green single crystals had grown in form of large sprays that look like snowflakes. Anal. calcd. for U6O54N4C20H64 (5) C, 9.06%; H, 2.43%; N, 2.11%. Found C, 9.10%; H, 2.12%; N, 2.01%. FT-IR: 3010 (w), 2970 (w), 2950 (w), 2360 (m), 2330 (m), 2060 (w), 2030 (w), 1740 (vs), 1660 (w), 1640 (w), 1630 (w), 1560 (w), 1510 (w), 1480 (w), 1470 (w), 1440 (m), 1370 (vs), 1230 (vs), 1220 (vs), 1090 (w), 901 (w), 787 (w), 667 (m), 606 (w), 598 (w), 538 (s), 528 (s). Yield: 24.7 mg (0.00992 mmol), 35.4%.

For single crystal X-Ray structural analysis, small amounts of the obtained crystalline materials were transferred into 7 mL scintillation vials without any purification. Attempts to rinse and purify product materials commonly resulted in the destruction of single crystals and seemed to transform products into different materials, even when a similar THF/EtOH/H2O solvent mixture was used for rinsing purposes, as the one that was employed in the experiments. For crystallography the crystals remained in the original mother liquor and were only taken up in oil right when mounted in the cold stream on the goniometer. Small samples of the remaining materials were dried at room temperature by leaving the open vial in the draft of a fume hood. A fraction of the dry samples was subjected to FT-IR spectroscopy.

Topological Analyses. Topological analyses were performed by the ToposPro Team using the ToposPro program package and the TTD collection of periodic network topologies.76 The RCSR threeletter codes were used to designate the network topologies.77 Those nets that are absent in the RCSR are designated with the Topos NDn nomenclature, where N is a sequence of coordination


10

Page 11 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


numbers of all non-equivalent nodes of the net, D is periodicity of the net (D=M, C, L, T for 0,1-,2-,3-periodic nets), and n is the ordinal number of the net in the set of all non-isomorphic nets with the given ND sequence.78 Coordination mode or connectivity of linkers to metal atoms in coordination compounds is characterized with the notation Lmbtkpghon. The symbol L is a letter M, B, T, K, P, G, H, O, or N designating the number (1, 2, 3, …, 9) of donor atoms that are coordinated to the metal atoms (A). Integers m, b, t, ... are equal to the number of metal atoms connected to one, two, three, ... donor atoms.79

X-ray Structure Determination. Intensity data for crystals of all compounds were collected on a Bruker D8 Quest singlecrystal X-ray diffractometer equipped with a complementary metal–oxide–semiconductor (CMOS) detector and a Bruker Triumph curved graphite MoKα X-ray source (λ= 0.71073 Å). Single crystals were mounted in cryoloops using paratone-n oil and cooled in-situ to 100 (2, 3 and 5), 107 (1) and 173 (4) K for data collection. Frames were collected, reflections were indexed and processed, and the files scaled and corrected for absorption using SADABS.80 The space groups were assigned and the structures were solved by direct methods using XPREP81, 82 and SHELXS-97 within the SHELXTL suite of programs and refined by full matrix least squares against F2 with all reflections using Shelxl 2016 utilizing the graphical interface Shelxle.83-86 If not specified otherwise H atoms attached to carbon and nitrogen atoms and hydroxy hydrogens were positioned geometrically and constrained to ride on their parent atoms, with carbon hydrogen bond distances of 0.95 Å for alkene and aromatic C-H, 0.99 and 0.98 Å for aliphatic CH2 and CH3, 0.88 for N-H and 0.84 Å for OH moieties, respectively. Methyl and hydroxy H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Uiso(H)


11


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 74

values were set to a multiple of Ueq(O/C/N) with 1.5 for CH3 and OH, and 1.2 for C-H, CH2 and N-H units, respectively. Complete crystallographic data, in CIF format, have been deposited with the Cambridge Crystallographic Data Centre. CCDC 1556078-1556082 contain the supplementary crystallographic data for this manuscript. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. For compound 1, a THF molecule hydrogen bonded to a uranium coordinated water molecule is disordered. It was refined as distributed over three positions. All three moieties were restrained to have similar geometries, and chemically equivalent bond distances within the THF molecules were restrained to be similar. Disordered atoms closer than 1.7 Å were restrained to have similar Uij components of their ADPs. O2B was restrained to be at a distance of 2.0(2) Å from one of the water H atoms. Subject to these conditions the occupancy rates refined to 0.322(4), 0.310(4) and 0.368(4). Reflection 0 1 1 was affected by the beam stop and was omitted from the refinement. For compound 2, the amino group of the 2-amino TP spacer is positionally disordered across an inversion center located at the center of the TP ring. It was refined as disordered with an H atom in a 1:1 ratio. Disordered solvate molecules occupy channels bisecting the unit cell diagonally. They were tentatively refined as partially occupied water molecules, with ADPs restrained to be close to isotropic (ISOR 0.01) and Uij components of ADPs to be similar for atoms closer than 1.7 Å. Water hydrogen atoms were omitted. The occupancy sum of nearby water O atoms was constrained to one. Subject to these conditions the occupancy rates refined to 0.192(3), 0.359(3), 0.218(3) and 0.230(3). Reflection 0 0 2 was affected by the beam stop and was omitted from the refinement.


12

Page 13 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For compound 3, substantial disorder of the uranium framework and unresolved solvent/sodium cation disorder is observed. The structure features four crystallographically independent terephthalate bridging units. One is located in a general position (O10-O13, C1623). One is located on an inversion center (O2, O3, C1-C4). One is located on an inversion center and oriented along a twofold axis (O4, C5-C7). The final TP entity is disordered around the intersection of two mirror planes and a twofold axis (O6-O9, C8-C15). This latter TP unit was refined as disordered over four symmetry equivalent positions with each one quarter occupancy. Its geometry was restrained to be similar to that of the TP spacer in the general position. In addition, the phenyl ring plus the carboxylate C atoms as well as the carboxylate group and the ipso carbon atoms were each restrained to lie within one plane. Disordered atoms of this unit were subjected to a rigid bond restraint (RIGU in Shelxl), and were restrained to be close to isotropic, and ADPs of several substantially correlated atoms were constrained to be identical (O6-O9, C8 and C15). The substantially different positions of the oxygen atoms within the disordered moieties induce a shift of the UO2 unit they are bonded to, and this unit was refined as disordered over two positions shifted along the axis of the O=U=O unit. The U=O distances in the two units were restrained to be similar in length, and ADPs of the two oxygen atoms were constrained to be identical. The disorder does to a smaller degree extend to the other TP units and the second UO2 moiety. Variations are however not well enough resolved for a meaningful refinement. Some additional constraints and restraints were applied: U1 and O1 were constrained to have identical ADPs as were C23, O12 and O13. Atoms O5, O12 and O13 were restrained to be close to isotropic. The structure contains solvent accessible voids of 2284 Å3 combined, or ca. 24.6% of the unit cell volume. The residual electron density peaks were not arranged in an interpretable


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 74

pattern, and no meaningful disorder and solvent model could be conceived. The cif and fcf files were thus corrected for using reverse Fourier transform methods with the SQUEEZE routine87 as implemented in the program Platon. The resultant files were used in the further refinement. (The FAB file with details of the Squeeze results is appended to the cif). The Squeeze procedure corrected for 939 electrons within the solvent accessible voids. For compound 4, sodium cations and water molecules are disordered with each other. A sodium ion octahedrally coordinated to four carboxylate oxygen atoms (2 x O3, 2 x O4) was set to be one third occupied for charge balance. The coordinated water molecules (O6) were set to the same occupancy. In the absence of the sodium ion a water molecule is located close to the sodium ion position. It was set to be 2/3rd occupied. Another water molecule, O7, is H bonded to either of the other water molecules, inducing disorder of its H atoms. All water H atom positions were restrained based on hydrogen bonding considerations. The structure was refined as a 4component twin by merohedric twinning emulating high symmetry cubic and by inversion. The BASF values refined to 0.003(8), -0.01(1) (i.e., zero) and 0.085(8). I.e., the twin domain created by emulation of the high symmetry cubic setting (TWIN 0 1 0 1 0 0 0 0 -1) is always also inverted. For compound 5 several solvate water molecules are 1:1 disordered due to the water molecule of O13 being incompatible with its counterpart created by a rotinversion axis (O...O distance of 2.18 Å). The 1:1 disorder extends to O11 and O12, which have slightly different positions than their symmetry created counterparts due to the presence or absence of hydrogen bonds to half occupied O13. O12 and its symmetry created counterpart O12B were constrained to have identical ADPs. O11 was restrained to be close to isotropic. Water H atoms were placed based on difference electron densities and refined with O-H and H...H distance restraints of


14

Page 15 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.84(2) and 1.36(2) Å. Additional H...O distances restraints were applied based on hydrogen bonding considerations. H atom distances were initially refined with a slight damping factor. In the final refinement cycles H atoms of disordered water molecules were set to ride on the carrying oxygen atom. The structure was refined as a 2-component inversion twin; BASF value 0.039(8). Figures displaying structural motifs were created using CrystalMaker® 9.2 for Mac as well as the ToposPro package.

FT-IR Spectroscopy. IR spectra were collected on a Thermo Scientific Nicolet iS5 FT-IR Spectrometer using a Golden Gate Diamond ATR unit with ZnSe lenses. Spectral resolution was typically 4 cm-1, and average data sets included 64 scans. We used the following abbreviations to describe the observed vibration modes: very strong (vs), strong (s), medium (m), weak (w), shoulder (sh), and broad (br).

Elemental Analysis. Elemental analyses (EA) were performed by Midwest Microlab LLC, using an Exeter Analytical CE-440 CHNOS elemental analyzer. Elemental analysis data did corroborate well with the single crystal X-Ray structure of 5. For 1, 2, 3, and 4 EA data were off, which we attribute to the fact that we were not able to clean the product materials well for the reasons given above. In most instances we presume that impurities mostly stem from unreacted starting materials, as evidenced by presence of traces of nitrogen for products that do not contain nitrogen as part of their composition (1, 4) or excess nitrogen in N-containing products (2).


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48

Page 16 of 74

Table 1. Crystal Data and Summary of Data Collection and Refinement for Compounds 1- 5 Formula

[[UO2](TP)(H2O)2] ·2THF (1)

[[UO2](TPNH2)(H2O)2] ·2H2O (2)

Na2[[UO2]2(TP)3] ·9H2O (3)

Na2[[UO2]2(Glut)3] ·8H2O (4)

U6(NO3)4(Glut)4(O)4(OH)4(H2O)6 ·12H2O (5)

Fw(g/mol)

614.38

515.18

1240.52

1120.46

2652.93

a (Å)

11.456(4)

17.0562(13)

34.464(3)

14.6636(10)

13.3846(10)

b (Å)

11.456(4)

9.1844(7)

19.6386(18)

14.6636(10)

13.3846(10)

c (Å)

14.509(5)

12.9404(10)

13.7087(13)

14.6636(10)

15.7472(12)

α (°)

90

90

90

90

90

β (°)

90

90

90

90

90

γ (°)

120

90

90

90

90

V (Å3)

1649.0(12)

2027.1(3)

9278.3(15)

3153.0(6)

2821.1(5)

Crystal system

trigonal

orthorhombic

orthorhombic

cubic

tetragonal

Space group

P3121

Pccn

Cmcm

I213

I4

Z

3

4

8

4

2

Dc (Mg•m-3)

1.856

1.688

1.776

2.360

3.123

µ (mm-1)

7.427

8.039

7.065

10.378

17.292

F(000)

876

936

4640

2088

2392

T (K)

107(2)

100(2)

100(1)

173(2)

100(1)

Refln. Indep.

3374

4452

4679

2345

5362

Refln. I>2σ(I)

3317

2554

3479

2292

5038

Rint

0.0300

0.0702

0.0753

0.0452

0.0349

R1 (I>2σ(Ι))

0.0124

0.0363

0.0611

0.0179

0.0179

wR2 (I>2σ(Ι))

0.0287

0.0818

0.1882

0.0376

0.0388


16

Page 17 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


RESULTS AND DISCUSSION Synthesis. The treatment of [UO2(NO3)2]·6H2O with sodium terephthalate (Na2TP), sodium 2aminoterephthalate (Na2TPNH2), sodium 2-nitroterephthalate (Na2TPNO2), or sodium-glutarate (Na2Glut) under the experimental conditions at room temperature generated water insoluble products that formed single crystals. The form of these materials ranged from loose, thin, long individual needles to large rectangular blocks, and cubes. 1 and 2 contain coordinated water molecules as well as, uncoordinated waters and/or THF, found as guest entities within the interstices. 3, 4, and 5 contain only interstitial water molecules, as well as interstitial sodium cations in 3 and 4.

Solid State Structures. Herein we showcase the synthesis and structural characterization of five uranium coordination polymers, which we obtained via slow diffusion methods at room temperature. These coordination polymers assemble as 3D and 2D networks as well as 1D chains. While we employed two different di-carboxylate spacer units in our experiments we were only able to integrate one kind of linker at a time, contrasting previous work with trivalent lanthanide compounds.75,

88, 89

The structural geometry of the UO22+ entity limits the construction of

extended networks, and it comes at no surprise that it is more challenging to create a 3Dinterlinked network when working with the uranyl species. As a matter of fact, only when working with the quite flexible glutarate spacer unit were we able to obtain an interlinked network, incorporating the uranyl species in a 3D fashion without the expansion of dimensionalities via hydrogen bonds. Since Giesting’s and Burns’ review article on the


17


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 74

classification of carboxylates, and uranyl polyhedral geometries in uranyl-organic compounds,68 numerous other articles referencing a large number of uranyl-coordination networks have been reported;

60, 65-67

In some cases, uranyl forms individual 8-coordinated polyhedra,50 while in

others the coordination polyhedra assemble in various forms of clusters.53, 69 Additionally it has been reported that uranyl is capable of simultaneously integrating multiple linking entities.48, 90 All the uranyl products reported here form networks based on individual UO8-coordination polyhedra that are connected entirely via the corresponding linking system without any cluster formation. These arrangement produce 8-coordinate UO8 polyhedra, which are represented by one of the three very common coordination geometries for uranyl-organic compounds; the hexagonal bipyramid.67 The linear uranyl units in 1 - 4 exhibit the expected bond angles close to 180˚ (ranging between 177.5(6) ˚ and 180.0(3) ˚) and uranyl oxo bond distances ranging between 1.730(15) Å and 1.772(5) Å.68

[[UO2](TP)(H2O)2]·2THF (1) 1 crystallizes in the trigonal crystal system with space group P3121. The structure assembles as an interwoven network with infinite 1-dimensional (1D) linear chains of [[UO2](TP)(H2O)2]n. These chains stretch in three directions with 2C1 topology, as shown in Figure 1. Two THF molecules per [[UO2](TP)(H2O)2] segment are found between chains. Carboxylate oxygens of the TP-units chelate on opposite sides of the uranyl-entity in transfashion. Two molecules of water also coordinate in trans fashion on opposite sides of UO22+. This arrangement results in the linear expansion of these chains. The six O-atoms in the equatorial plane consist of the two trans carboxylate groups from two different


18

Page 19 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


terephthalate entities with U-O bond distances of 2.444(2)Å on one side of the moiety and 2.505(2)Å on the other side, as well as 2.460(2)Å for the two coordinating water molecules that are also arranged in trans-fashion.

a)

b) Figure 1. a) A string of linear [UO2](TP)(H2O)2-segments, in which UO8 coordination polyhedra with the geometry of a hexagonal bi-pyramid are interlinked via terephthalate entities, and b) simple chain with 2C1 topology.

This data falls into the expected range for equatorial U-O bonds in uranyl-organic compounds.68 The individual [[UO2](TP)(H2O)2]n-polyhedra are interlinked by the terephthalate units forming straight 1D-chains (Figure 1). These chains stretch in three different directions along the a- and b-axes (120˚ angles) as well as dissecting the ab-plane with a 60˚ angle. Figure 2a demonstrates how the individual linear chains of [[UO2](TP)(H2O)2]n stack in three layers along the c axis arranging in 60˚ angles towards each other within the ac plane. They are stabilized by hydrogen bonds resulting in a 3D-structure with a uninodal 4-coordinated (uom) network as shown in Figure 2b. This type of coordination polymer has been previously described by Zou et al. for cadmium metal centers, chelated by pyridine-2,4,6-tricarboxylate linkers.91 Hydrogen bonds between water hydrogens of one UO8-polyhedron with the terephthalate carboxy-oxygen of the next layer (O-H distance of 2.007 Å) hold the individual strings in place resulting in the


19


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 74

intermeshed 3D-structure. This arrangement exposes the terephthalate entities to some moderate strain as torsion angles between the carboxylate groups and the benzene rings are between 10.2˚ and 18.6˚.

a)


20

Page 21 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


b) Figure 2. Structural arrangement of 1, forming intermeshed 1D channels. (grey = U, black = C, red = O (from carboxylate units, uranyl-oxygens, maroon = O (from H2O), white = H). a) View onto the ab plane showing infinite 1D chains of [[UO2](TP)(H2O)2]n stretching in three directions. b) Individual chains stacking along the c-axis are oriented with 60˚ angles towards each other forming a 3D-structure with hydrogen bonds between coordinating water molecules as well as carboxylate oxygens of adjacent chains stabilizing the 3D-arrangement of this network (left). The resulting overall topology creating a uninodal uom network (right).91

[[UO2](TPNH2)(H2O)2]·2H2O (2) 2 crystallizes in the orthorhombic crystal system with space group Pccn. The structure assembles as an interwoven network with 2-dimensional (2D) layers of [[UO2](TPNH2)(H2O)2]n, forming infinite zig-zag chains that dissect the ab plane by 45˚ angles. Interstitial water is found between layers of zig-zag chains directed along these chains in a wave form. Two H2O molecules per [[UO2](TPNH2)(H2O)2] segment are found between chains. This structure is related to 1, as infinite [[UO2](TPNH2)(H2O)2]n segments in 2 are formed, which also exhibit the 2C1 topology for the simple chains. In 2, however, carboxylate oxygen atoms of TPNH2-entities chelate in cis-fashion as opposed to the trans arrangement in 1. Accordingly, two H2O molecules coordinate in cis-manner on the side opposite of the TPNH2-units, resulting in a characteristic


21


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 74

zig-zag assembly (Figure 3). Severance et al. reported a uranyl 2-nitroterephthalate compound that also assembles as a 3D coordination polymer. In their compound, there are two crystallographically distinct uranium central atoms that are connected via cation-cation interactions resulting in the formation of U2O15-clusters. UO8-coordination polyhedra are connected through corner sharing with the oxygen atom facilitating the corner belonging to the axial uranyl unit of one uranium central atom and to the equatorial coordination sphere of the other.92 While their uranyl coordination polymers also exhibit a cis-arrangement of 2nitroteraphthalste spacers, the coordination mode is significantly different as compared to 2, since their clusters incorporate bridging carboxylate groups. In contrast, 2 incorporates only bidentate chelating carboxylate groups and individual UO8-coordination polyhedra are interlinked by the 2-aminoterephtahle entity. The six O-atoms in the equatorial plane are made up of the two cis-carboxylate groups stemming from two different 2-aminoterephthalate spacer units with U-O bond distances of 2.475(3) Å and 2.482(4) Å respectively, as well as 2.451(3) Å for the two coordinating water molecules, also arranged in cis-fashion. These numbers agree well with previously observed data in uranyl-organic compounds.68 Figure 4 shows one of the 2D layers illustrating the cis-arrangement of TPNH2 and water molecules as part of the coordination polyhedra. This arrangement seems to cause some mild strain on the TPNH2 spacer units as torsion angles between carboxylate groups and benzene rings are measured between 8.2˚ and 11.4˚. The interwoven structure is held in place via hydrogen bonds between coordinating water molecules and carboxylate oxygens of adjacent zig zag-strings. Moreover, hydrogen bonds between amino groups and uranyl(VI) oxo ligands of the adjacent chain add to the stability of the resulting 3D-structure with an overall 2-nodal 4-coordinated pts network topology (Figure 5). In


22

Page 23 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1 and 2 the carboxylate groups on both sides of the linker entity dock to the uranyl(VI) unit with respectively both oxygen atoms in the equatorial plane resulting in the K02 coordination mode.

Figure 3 Structural arrangement of 2, forming interwoven 2D layers. (grey = U, black = C, red = O (from carboxylate units and uranyl-oxygens), maroon = O (from H2O), white = H). View onto the ac plane showing infinite zig-zag chains of [[UO2](TPNH2)(H2O)2]n dissecting the ab plane by 45˚ angles. Hydrogen bonds (black and white) tying together adjacent zig zag-strings.


23


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 74

Figure 4 2D layer in 2, demonstrating the zig-zag nature of individual chains directly resulting from the ciscoordination of carboxylate groups and water molecules to the uranium metal center (grey = U, black = C, red = O (from carboxylate units and uranyl-oxygens), maroon = O (from H2O), white = H). Like in 1, simple chains possess 2C1 topology.


24

Page 25 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 5 Two adjacent strings of simple zig zag-chains in 2, stabilized by hydrogen bonds (black and white) between coordinating water molecules and carboxylate oxygens of the adjacent zig zag-string. Additional hydrogen bonds between amino groups and uranyl(VI) oxo ligands of the adjacent chain contribute to the corresponding interwoven layers to be held in place (grey = U, black = C, red = O (from carboxylate units and uranyl-oxygens), maroon = O (from H2O), white = H) (left). The resulting structure assembles with a 2-nodal 4-coordinated pts network topology (right).

Na2[[UO2]2(TP)3]·9H2O (3) 3 crystallizes in the orthorhombic crystal system with space group Cmcm. The structure assembles as infinite 2-dimensional anionic layers of [[UO2]2(TP)3]2-n, within the ab plane. Nacations and water molecules are found to occupy infinite channels that run along the c axis. In order to maintain electroneutrality, two Na+-ions are assigned for every [UO2]2(TP)3 entity. The structure is best described as being built around two crystallographically independent uranium(VI) ions (U(1) and U(2)) that form the centers for individual UO8-coordination polyhedra. The 2D-layers are built by one of the two independent uranium(VI)-ions respectively as shown in Figure 6a. Layers pile in alternate fashion with regard to the two independent uranium central atoms (U(1) is shown in dark grey, and U(2) in light grey). Figure 6b demonstrates how layers, incorporating U(2), assemble from UO22+ ions and terephthalate spacers interconnecting UO8 coordination polyhedra to form hexagonal rings (honeycombs) of [UO2]6(TP)6, which are infinitely linked within the ab plane. Thus, each UO8-polyhedron resides as the center of a trigonal planar arrangement of three terephthalate linkers around it.


25


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 74

a)

b) Figure 6. Structural arrangement of 3, forming parallel 2-dimensional layers in the ab plane. (dark grey = U(1), light grey = U(2), black = C, red = O (from carboxylate units and uranyl-oxygens), Na+, H2O, and H left out for clarity). a) View from the side onto the infinite 2D layers of [[UO2]2(TP)3]2-n connecting in three directions around each uranyl-entity within the layers, while accommodating H2O molecules and sodium cations in channels running down


26

Page 27 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


the c axis (not shown). b) View onto two offset layers in the ab plane showing the honeycomb arrangement of TP entities in the equatorial plane around UO22+-units.

Moreover, each polyhedron, thereby, fuses three adjacent honeycombs resulting in the overall topology of a uninodal 3-coordinate honeycomb (hcb) motif, where nodes correspond to UVI, and edges are TP2- spacers (Fig. 7). The hcb net is present in more than 3200 2D-coordination polymers.

a)

b) Figure 7. a) The hcb motif of simplified structure 3. b) π-π interactions between two layers with respectively crystallographically independent uranium metal centers (dark grey = U(1), light grey = U(2), black = C, red = O (from carboxylate units and uranyl-oxygens)).


27


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 74

The layers, incorporating U(1), are created via the exact same assembly. U(1) layers superimpose, enclosing one U(2) layer in-between. However, every other U(2) layer superimposes by enclosing two U(1) and one U(2) layers, as the next U(2) layer is shifted in the b direction. Thus, the anionic layers are packed as ABAB… into a 3D structure by π-π interactions (stacking) between benzene rings (Fig. 7b). The metal-containing SBUs, U(COO)3, are identical to the ones found in structure 4. This type of layering has been discussed in detail before93 and Go et al. published a compound identical to 3, with the exception that sodium counter ions in 3 are replaced by ammonium ions in their compound.94 The UO8 polyhedra of the crystallographically independent uranium metal centers differ only slightly with regard to angles. Similar deviations in the magnitude of the bond distances can be observed; however, we note that when the uncertainties in the measurements are considered, these values are equivalent at 1 σ. For example, the bond lengths between the U(1) atom and both uranyl oxygens are 1.747(9) Å, while the corresponding bond distances for the U(2) atom and its uranyl oxygens measure 1.730(15) and 1.751(14) Å. The uranyl bond angle for the U(1) uranyl turned out to be nearly linear with 179.5(5) ˚, while the U(2) counterpart was determined to be 177.5(6) ˚. The bond distances between the U(1) central atom and the surrounding six carboxylate oxygens lie between 2.456(8) and 2.490(9) Å, and the bond distances for the U-2 atom and the six carboxylate oxygens are measured between 2.426(11) and 2.51(4) Å. The structure of 3 is similar to that of 1 and 2, in that all of the compounds contain infinite [[UO2](TP)3]n. 3 differs in that the uranyl carboxylate oxygen atoms from the TP-entities saturate the entire uranium equatorial coordination environment, exhibiting the K02 coordination mode (Figure 6b).


28

Page 29 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


The coordination of the terephthalate spacers seems most relaxed for the U(2) layers as practically no torsion angle is observed between the benzene rings and the carboxylate groups after accounting for the disorder, while the U(1) layers have some torsion angles for these entities of 17.6˚.

Na2[[UO2]2(Glut)3]·8H2O (4): 4 crystallizes in the cubic crystal system with space group I213. This structure assembles as a 3D-coordination network, which can be attributed to the flexibility of the glutarate linker. The U-metal centers form UO8 coordination polyhedra, of which the 6 equatorial O–atoms stem from three different carboxylate groups. Thus, in this compound only interstitial water molecules are present. Figure 8 illustrates the linker and coordination environment around individual UO8polyhedra, connecting one coordination polyhedron to three others via three glutarate entities. It becomes apparent that the flexibility of the glutarate entity allows for the 3D interconnection of 4. While the rigidity of the TP and TPNH2 units prevents a direct 3D connection without the stabilizing effects of hydrogen bonds of the uranyl coordination centers in 1 and 2, the glutarate unit, despite its relatively short length, connects these coordination polyhedra beyond a 2dimensional system as can be seen in Figure 8b. The corresponding center polyhedron and the three connected units have all different orientations in space, resulting in the 3D-network. As observed for the previous structures the carboxylate units of the linkers have the coordination mode K02.


29


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

a)

Page 30 of 74

b)

Figure 8. a) Structural arrangement of 4, forming a 3D coordination polymer. View onto the “ac” plane without interstitial Na+ and H2O for clarity. b) Linker environment of one UO8-coordination polyhedron linking to three other UO8 units via three glutarate entities. (grey = U, black = C, red = O (from carboxylate units and uranyloxygens), and white = H).

Na+-ions are found within the interstices, forming distorted NaO6 octahedra as coordination polyhedra. Four of these oxygen atoms stem from two carboxylate units and the remaining two from interstitial water molecules, as shown in Figure 9. Sodium ion and and water molecule occupancies were not discretely resolved, such that the sodium ion was set to be one third occupied (for charge balance), and the coordinated water molecules were set to the same occupancy. In the absence of the sodium ion a water molecule is located close to the sodium ion position. It was set to be 2/3rd occupied (more details can be found in the supporting information).


30

Page 31 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 9. Na+ cations occupying octahedral positions with four oxygen atoms from different glutarate entities and two water molecules.

Bond angles and bond lengths for the UO8-coordination polyhedra in 4 are very close to those found for the other compounds. In this compound, the six O-atoms in the equatorial plane are all equivalent and consist of three carboxylate groups from three different glutarate spacers with UO bond distances of 2.422(3) Å and 2.497(3) Å, respectively. This data also falls into the expected range for equatorial U-O bonds in uranyl-organic compounds.

Figure 10. The srs net is merged with the initial network, not showing sodium cations and water molecules for simplicity (left) and a general view of the srs net (right).


31


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 74

The overall topology was determined as a uninodal 3-c srs (SrSi2) net that has been detected in 281 structures before (Fig.10). The metal carboxylate SBUs, Me(COO)3, were found in 2649 coordination polymers (1-, 2-, 3-dimensional), of which 99 incorporate UVI ions. These SBUs are identical to the ones we described for 3. Kim et al. and Serezhkina et al. both reported glutarate containing structures with the same U(COO)3 SBUs with ladder-like chains.95, 96 Benetollo et al. described one that is composed of a linear 1D-coordination polymer97 and Borkowski et al. reported a structure with a layered motif.90 Most recently Novikov et al. presented several uranyl glutarates. Two of them form 2D-layered structures that are further extended into 3D-networks through hydrogen bonds between layers, water molecules and ammonium ions. Some of the other structures reported in that work extend as 1D chains, however, alkaline metal counter ions between chains increase their dimensionality through edge and corner sharing between coordination polyhedra of various alkaline metal counter ions with the UO8-polyhedra.98

U6(NO3)4(Glut)4(O)4(OH)4(H2O)6·12H2O (5) When the reaction between [UO2(NO3)2]·6H2O, Na2TP, and Na2Glut involved short reaction time, compound 1 was obtained. In contrast, long reaction times – with these same reagents – generated 5. This compound crystallizes in the orthorhombic crystal system with space group I4. This structure assembles as a 3D-coordination network, which is a result of the flexibility of the glutarate entity. Moreover, the rather restrictive uranyl(VI) unit was replaced by +4 uranium cations, allowing for higher coordination numbers and more extensive connectivity. We are uncertain what caused the reduction of U(VI) to U(IV). The reaction mixture was kept for one year and it was after that long period of time that the green crystals of this product were observed. A possibility could be that the solvent mixture, which contained ethanol and THF


32

Page 33 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


may have allowed for a slow reduction to occur while exposed to ambient sunlight. It has been known for decades that photo reduction of U(VI) to U(IV) can take place in alcoholic solutions.99, 100 In Figure 11a) we depict the view onto the ab plane, showing the interlinkage of uranium-central atoms via hydroxy-anions (maroon O-atoms), glutarate linkers (black tetrahedra), and the construct of large clusters involving six U-atoms. This structure incorporates two crystallographically independent uranium(IV) metal centers, U(1) (dark grey) and U(2) (light grey). All U4+-ions are surrounded by nine oxygen atoms, forming UO9-coordination polyhedra. The geometry of the U(1)O9-polyhedra can be seen as trigonal prisms incorporating a minimal level of distortion with caps on each of the three faces. The U(2)-polyhedra can be assigned the same geometry relating them to the UCl3 structural type.101 It needs to be noted however, that a somewhat higher level of distortion is observed for the trigonal prisms regarding the U(2)-central atoms. For descriptive purposes we will treat both as monocapped squared antiprisms, although these exhibit rather large levels of distortion under this alternative geometric shape. The quite distorted square base of each polyhedron is constructed of two hydroxy anions (maroon) and two oxo-groups. These facilitate linkage between two U(1)-atoms and four U(2)-atoms to assemble as U6O38-clusters, whereby two U(1)O9-polyhedra are positioned with their square bases facing each other and the terminal capping O-atoms (maroon, H2O) are facing in opposite directions, while aligning with the c-axis. The square bases are offset by 90° about the c-axis. Figure 11b) shows how four U(2)O9-polyhedra (light grey) are fused with the two U(1)O9-polyhedra (dark grey) via corner and edge sharing through the oxo and hydroxy groups (orange and maroon), leaving an octahedral hole in the center of the resulting U6O38-cluster.


33


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

a)

Page 34 of 74

b)

Figure 11. a) View of the structural arrangement in 5, forming a 3D-coordination polymer. Large clusters, built from 6 U-central atoms are interlinked through glutarate linkers. b) Fusion of two U(1)O9 and four U(2)O9 – polyhedra via edge sharing of oxo and hydroxy groups (orange and maroon), creating a U6O38-culster with an octahedral hole in the center (dark grey, U(1), light grey = U(2), black = C, red = O (from carboxylate units), orange = O (from µ3-oxo groups) maroon = O (from µ3, terminal hydroxide, and terminal H2O), purple = O (from nitrate), white = H, blue = N).

The respective two oxo and hydroxy groups (orange and maroon), building the square base of the U(1)O9-polyhedra coordinate in µ3-fashion to three central U-atoms (one U(1)-atom and two U(2)-atoms). Thus, they facilitate the corner-sharing of two U(2)O9 and one U(1)O9–polyhedra. Neighboring U(2)O9-polyhedra are rotated by 180°, resulting in an arrangement, in which oppositely positioned U(2)O9-polyhedra are aligned with each other. The remaining five coordinating oxygen atoms of the U(1)O9-polyhedra originate from two carboxylate O-atoms and three terminal water molecules (red, and maroon). One of the terminal water molecules occupies the cap on the upper square plane of the U(1)-square antiprism (O(11)). The remaining five oxygens of the U(2)O9-polyhedra stem from three carboxylate O-atoms and two nitrate Oatoms, of which one nitrate oxygen occupies the cap of the upper square planar face. Figure 12a


34

Page 35 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


illustrates how U6O38-clusters are interlinked via glutarate entities in all three dimensions. Each glutarate entity spans between U6O38-clusters by chelating in a bidentate fashion to two adjacent U(2)-central atoms on one side, and also by chelating in a bidentate mode on the other side to one U(1)-metal center and its adjacent U(2)-central atom. Thus, the glutarate spacers dock to the metal centers via the K4 coordination mode. On the lower side of each cluster four glutarate units connect to four other clusters, which on their part connect to four clusters respectively. Therefore, each cluster has eight glutarate carboxylate groups docking from all directions, allowing the system to extend as a 3D-network (shown in Figure 12b). The motif resulting from this arrangement with glutarate units extending towards all directions resembles an octopus and its tentacles as shown in Figure 12b. Two O-atoms of each nitrate anion chelate in a bidentate fashion to one U(2)-central atom, while the terminal nitrate O-atom is directed towards the interstices between U6O38 clusters. This renders spacious cavities in the center of six U6O38clusters, connected via glutarate. These clusters are based on U6O8-cages that result from the edge and corner sharing of the six uranium metal centers with the eight µ3-coordinated oxo and hydroxy groups.


35


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

a)

Page 36 of 74

b)

Figure 12. a) Linkage of U6O38-clusters in three dimensions. b) Docking of eight glutarate units from all directions onto one U6O38-cluster (dark grey, U(1), light grey = U(2), black = C, red = O (from carboxylate units), orange = O (from µ3-oxo groups) maroon = O (from µ3, terminal hydroxide, and terminal H2O), purple = O (from nitrate), white = H, blue = N).

The topology of the underlying net in standard representation is classified as a 3,3,4,6,7-c net, which is a new topological type that has not been detected in crystal structures before. The cluster simplification procedure (alternative method for topological analysis) separates clusters (or SBUs) by ring size criteria. Based on the result of this procedure structure 5 is divided into interclusters as part of the glutarate (skeleton of C) and U6C8N4O42 SBUs that consist of U6O8 clusters, terminal ligands and carboxylate groups. The simplification of SBUs into their mass centers leads to a uninodal 8-c net called body centered cubic or bcu; 8/4/c1; sqc3 (Figure 13). The TTO-collection includes 444 structures with the bcu network in standard cluster representation.


36

Page 37 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 13. The node of the bcu net is merged with U6C8N4O42 an SBU (left) and a fragment of the overall bcu net (right).

Falaise et al. described four compounds with the bcu network type and similar U6O8-clusters, serving as SBUs for the assembly of their resulting 3D-coordination networks. Instead of glutarate, the U6O8 clusters in their structures connect through fumarate, terephthalate, 2,6naphthalene-dicarboxylate, and 4,4’-biphenyldicarboxylate linkers.49 They further obtained a 3D thorium terephthalate network, Th6O4(OH)4(H2O)6(TP)6·6DMF·12H2O, which is based on related Th6O8-clusters.48 These U6O8-cage clusters have been detected as far back as the 1950s, when Lundgren reported the synthesis of U6O4(OH)4(SO4)6.102 Similar U6O8-cage clusters were detected in a uranium phosphate in the 1990s.103 Later, a larger number of compounds incorporating similar An6O8-cages with An = Th or U were created,104-108 as nicely laid out in Burn’s 2013 review article.109 After accounting for the four U(1)-O(4) and the twelve U(2)-O (O(1), O(2), O(3)) bonds that stem from carboxylate groups (red) and eight U(2)-O (O(8), O(9)) bonds, originating from nitrate (purple) for a given U6O38-cluster, the remaining 14 oxygen atoms were best


37


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 38 of 74

modeled as water, hydroxy, and oxo groups. Falaise et al. reported similar arrangements of oxygen atoms for their structures.49,

110

Four oxygen atoms were found to be oxo groups

(orange). These make up half the oxygens of the inner square bases as part of the U6O8 SBUs that coordinate in µ3-fashion to one U(1) and two U(2) central atoms (Figure 11b). Their bond distances were determined as 2.239(4) Å for two respective U(1)-O(6) bonds, 2.197(4) Å for U(2)-O(6), and 2.281(4) Å for the second U(2)-O(6) bond. These bond distances correlate well with literature values, which were reported as average U-O bonds between 2.20 and 2.27 Å for hexanuclear clusters.104, 108, 110-112 The remaining four µ3-coordinating oxygens are hydroxy groups (maroon), which are the other four inner square base oxygens that facilitate the edge and corner sharing between the six UO9polyhedra via µ3-coordination. The bond lengths of these µ3-coordinating hydroxy groups were measured as two (U(1)-OH(5) bonds with lengths of 2.479(4) Å, one U(2)-OH(5) bond of 2.423(4) Å, and the second U(2)-OH(5) bond with 2.451(4) Å. In the literature, average U-OH bond lengths were reported between 2.40 – 2.50 Å108, 110, 111 for similar clusters. The four oxygen atoms constituting the outer square bases of the U(1)O9-polyhedra are terminal water molecules. The remaining two oxygen atoms, which form the vertices for the caps of the outer square planes (also maroon), are also terminal water molecules. They possess the longest U(1)-OH2(11) bond lengths with 2.631(6) Å. Knope et al. demonstrated that similar hexanuclear Pu6O8 clusters can be obtained that show an identical motif with four µ3-oxo groups as well as four µ3-hydroxy groups. Individual PuO9coordination polyhedra are also capped with a terminal water molecule and have carboxylate oxygens docking to the clusters that stem from glycine units.113


38

Page 39 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Outlook. The products we obtained indicate that slow diffusion techniques at room temperature offer an alternative to hydrothermal synthetic approaches often employed for the creation of coordination polymers. This includes formation of uranyl-entity and uranium(IV) containing materials. Moreover, the uranyl-unit seems to be rather restrictive with regard to the incorporation of more than one type of spacer entity as opposed to trivalent lanthanide ions.88 The capping oxo groups associated with UO22+ limit coordination sites to the equatorial plane, making it more challenging to create multidimensional coordination networks. Consequently, compounds 1, 2, and 3, that integrate the rather rigid TP and TPNH2 spacer units formed 1D and 2D networks. Compounds 1 and 2 are further stabilized by hydrogen bonding, which impart 3dimentional connectivity throughout the structures. Usually, 3D-networks based on the uranyl unit and terephthalate derivatives or other rigid aromatic spacer systems are a result of cluster formation between multiple uranyl coordination polyhedra.53, 69 Only in 4 did the flexible glutarate linker allow for the connectivity necessary for a 3Dcoordination polymer in these uranyl compounds, without the necessity of hydrogen bonding. In our previous investigations of trivalent lanthanide terephthalates and lanthanide 2nitroterephthalates, we observed fairly crowded coordination networks with significant strain on the rigid spacer units, resulting in larger torsion angles ranging between 1.1˚ and 38.0˚ for the terephthalates114 and up to 90.4˚ for the lanthanide 2-nitroterephthalates.115


39


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 40 of 74

CONCLUSIONS Slow diffusion methods at room temperature have been used in isolating an array of uranium open frameworks that incorporate organic spacer units. The reaction conditions dissolving uranyl(VI) nitrate hexahydrate in water and bringing these solutions in contact with the corresponding linking systems dissolved in DI-water or a mixture of THF, ethanol, and DIwater. The topologies of the resulting extended 1D, 2D, and 3D-networks depended on (1) the identity of the spacer unit integrated into the uranium coordination sphere and (2) the number of carboxylate groups and water molecules (if any) that dock to uranium. In 1 – 3, the linear uranyl unit combined with the rather rigid terephthalate or 2-aminoterephthalate entity restricts the resulting networks to a maximum of 2 dimensions in compounds, as long as cluster formation between uranyl coordination polyhedra is absent.53, 69 Hydrogen bonding in 1 and 2, however, stabilizes the individual 1D and 2D -systems and ties them into overall 3D networks. The aromatic spacer systems undergo only small out of plane distortion without a significant disruption of the conjugate π-system. We observed maximum tilt angles between aromatic rings and the carboxylate groups of 18˚. This torsion is far below the threshold angle of approximately 60˚ at which the conjugation is commonly viewed as entirely disrupted.116 These compounds assemble as structures with higher symmetry levels than the lanthanide terephthalates which we described in a previous manuscript.114 The highest level of network connectivity as well as symmetry was realized for 4 and 5, with 4 crystallizing in the cubic crystal system and space group I213. Compound 5 (I4 space group) is unique in comparison to 1 – 4. It represents the compound in the series that involved reduction of the UO22+ precursor to UIV, despite no attempt to exclude air and moisture. While it is unclear what is being oxidized in this reaction, the combination of U4+ and glutarate provides


40

Page 41 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


an ideal environment for stabilizing uranium in the +4 oxidation state, which leads to higher uranium coordination numbers, and potentially contributes to the higher levels of connectivity. Spacer flexibility is also a factor, as glutarate provides three sp3-hybridized CH2-groups, allowing for the connection of uranium atoms in both 4 and 5. Overall, these results highlight the unique properties of the MOF framework for stabilizing low actinide oxidation states. Moreover, these results serve as motivation to further investigate f-element MOFs in an attempt to uncover unique f-element properties, reactivities, and structural motifs.

ASSOCIATED CONTENT Supporting Information. Crystallographic data, CCDC 1556078-1556082, was deposited with the Cambridge Crystallographic

Data

Centre

and

can

be

obtained

free

of

charge

via

www.ccdc.cam.ac.uk/data_request/cif.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]

ORCID: orcid.org/0000-0002-3478-630X


41


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 42 of 74

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was supported in part by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists (WDTS) under the Visiting Faculty Program (VFP). It was further supported under the Heavy Element Chemistry Program at Los Alamos National Laboratory (LANL, Kozimor, Boncella) by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy. LANL is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of U.S. Department of Energy (contract DE-AC52-06NA25396). We would like to thank Angelo State University for additional financial support through the Department of Chemistry & Biochemistry and the Faculty Research Enhancement Program as well as the Welch Foundation.


42

Page 43 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


REFERENCES (1) Chen, B.; Ma, S.; Hurtado, J.; Lobkovsky, E. B.; Zhou, H. C. Inorg . Chem. 2007, 46, 8490-8492. (2) Chen, B.; Wang, L.; Zapata, F.; Qian, G.; Lobkovsky, E. B. J. Am. Chem. Soc. 2008, 130, 6718-6719. (3) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469–472. (4)

Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem. Int. Ed. 2004, 43, 2334–2375.

(5)

Kitagawa, S.; Matsuda, R. Coordin. Chem. Rev. 2007, 251, (21-24), 2490-2509.

(6) Yaghi, O. M.; Chen, B. High gas adsorption in a microporous metal-organic framework with open-metal sites. 2006. (7) Zhao, S. N.; Song, X. Z.; Zhu, M.; Meng, X.; Wu, L. L.; Song, S. Y.; Wang, C.; Zhang, H. J. Dalton Trans. 2015, 44, (3), 948-954. (8)

Evans, O. R.; Lin, W. Acc. Chem. Res. 2002, (35), 511-522.

(9)

Fu, D. W.; Zhang, W.; Xiong, R. G. Dalton Trans. 2008, 3946–3948.

(10) Dietzel, P. D. C.; Morita, Y.; Blom, R.; Fjellvag, H. Angew. Chem. Int. Ed. 2005, 44, 6354–6358. (11)

Kahn, O.; Martinez, C. J. Science 1998, 279, 44-48.

(12) Férey, G.; Millange, F.; Morcrette, M.; Serre, C.; Doublet, M. L.; Grenèche, J. M.; Tarascon Angew. Chem. Int. Ed. 2007, 46, 3259-3263. (13) Liu, J.; Wachter, T.; Irmler, A.; Weidler, P. G.; Gliemann, H.; Pauly, F.; Mugnaini, V.; Zharnikov, M.; Woll, C. ACS Appl. Mater. Inter. 2015, 7, (18), 9824-9830. (14)

Goswami, S.; Jena, H. S.; Konar, S. Inorg. Chem. 2014, 53, (14), 7071-7073.

(15)

Herbst, A.; Khutia, A.; Janiak, C. Inorg. Chem. 2014, 53, (14), 7319-7333.

(16) Yang, T.; Cui, H.; Zhang, C.; Zhang, L.; Su, C. Y. Inorg. Chem. 2013, 52, (15), 90539059. (17)

Chen, D. M.; Ma, X. Z.; Shi, W.; Cheng, P. Cryst. Growth Des. 2015, 3999–4004.

(18) Sel, K.; Demirci, S.; Ozturk, O. F.; Aktas, N.; Sahiner, N. Microelectron. Eng. 2015, 136, 71-76. (19) Yang, J.; Wang, Z.; Hu, K.; Li, Y.; Feng, J.; Shi, J.; Gu, J. ACS Appl. Mater. Inter. 2015, 7, (22), 11956-11964.


43


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(20)

Page 44 of 74

Zhao, Z.; Hao, J.; Song, X.; Ren, S.; Hao, C. RSC Adv. 2015, 5, 49752–49758.

(21) Ma, D. Y.; Li, Z.; Xiao, J. X.; Deng, R.; Lin, P. F.; Chen, R. Q.; Liang, Y. Q.; Guo, H. F.; Liu, B.; Liu, J. Q. Inorg. Chem. 2015, 6719–6726. (22)

Nagata, S. K., K.; Sada, K. Chem. Commun., 2015, 51, 8614-8617.

(23) Ma, S.; Sun, D.; Wang, X. S.; Zhou, H. C. Angew. Chem. Int. Ed. 2007, 46, (14), 24582462. (24) Peterson, G. W.; DeCoste, J. B.; Fatollahi-Fard, F.; Britt, D. K. Ind. Eng. Chem. Res. 2014, 53, (2), 701-707. (25)

Li, B.; Chrzanowski, M.; Zhang, Y.; Ma, S. Coord. Chem. Rev. 2016, 307, 106-129.

(26) Fracaroli, A. M.; Furukawa, H.; Suzuki, M.; Dodd, M.; Okajima, S.; Gandara, F.; Reimer, J. A.; Yaghi, O. M. J. Am. Chem. Soc. 2014, 136, (25), 8863-8866. (27)

Ma, S.; Zhou, H. C. Chem. Commun. 2010, 46, (1), 44-53.

(28) Wang, T. C.; Bury, W.; Gomez-Gualdron, D. A.; Vermeulen, N. A.; Mondloch, J. E.; Deria, P.; Zhang, K.; Moghadam, P. Z.; Sarjeant, A. A.; Snurr, R. Q.; Stoddart, J. F.; Hupp, J. T.; Farha, O. K. J. Am. Chem. Soc. 2015, 137, (10), 3585-3591. (29) Zhang, H., Deria, P.; Farha, O.; Hupp, J.T.; Snurr, R. Energ. Environ. Sci. 2015, 8, 15011510. (30) Wen, H. M.; Wang, H.; Li, B.; Cui, Y.; Wang, H.; Qian, G.; Chen, B. Inorg. Chem. 2016, 55, (15), 7214-7218. (31) So, M. C. W., G.P.; Mondloch, J.E.; Hupp, J.T.; Farha, O.K. Chem. Commun. 2015, 51, 3501-3510. (32) Ikezoe, Y.; Fang, J.; Wasik, T. L.; Shi, M.; Uemura, T.; Kitagawa, S.; Matsui, H. Nano Lett. 2015, 15, (6), 4019-4023. (33) Ikezoe, Y.; Washino, G.; Uemura, T.; Kitagawa, S.; Matsui, H. Nat. Mater. 2012, 11, 1081-1085. (34) Chen, B.; Qian, G., Metal-Organic Frameworks for Photonics Applications. ed.; Springer: 2014. (35) Yu, J.; Cui, Y.; Wu, C. D.; Yang, Y.; Chen, B.; Qian, G. J. Am. Chem. Soc. 2015, 137, (12), 4026-4029. (36) Goesten, M. G.; Juan-Alcañiz, J.; Ramos-Fernandez, E. V.; Sai Sankar Gupta, K. B.; Stavitski, E.; van Bekkum, H.; Gascon, J.; Kapteijn, F. J. Catal. 2011, 281, (1), 177-187. (37) Jiang, J.; Gandara, F.; Zhang, Y. B.; Na, K.; Yaghi, O. M.; Klemperer, W. G. J. Am. Chem. Soc. 2014, 136, (37), 12844-12847.


44

Page 45 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(38)

Adam, J. L. Chem. Rev. 2002, 102, (6), 2461-2476.

(39) de Bettencourt-Dias, A.; Barber, P. S.; Bauer, S. J. Am. Chem. Soc. 2012, 134, (16), 6987-6994. (40) Luebke, R.; Belmabkhout, Y.; Weselinski, L. J.; Cairns, A. J.; Alkordi, M.; Norton, G.; Wojtas, L. A., K.; Eddaoudi, M. Chem. Sci. 2015, 6, 4095–4102. (41)

Neogi, S.; Bharadwaj, P. K. Polyhedron 2006, 25, (7), 1491-1497.

(42) Wang, C. G.; Xing, Y. H.; Li, Z. P.; Li, J.; Zeng, X. Q.; Ge, M. F.; Niu, S. Y. J. Mol. Struct. 2009, 921, 126–131. (43) Xue, D. X.; Belmabkhout, Y.; Shekhah, O.; Jiang, H.; Adil, K.; Cairns, A. J.; Eddaoudi, M. J. Am. Chem. Soc. 2015, 137, (15), 5034-5040. (44) Zhao, S. N.; Li, L. J.; Song, X. Z.; Zhu, M.; Hao, Z. M.; Meng, X.; Wu, L. L.; Feng, J.; Song, S. Y.; Wang, C.; Zhang, H. J. Adv. Funct. Mater. 2015, 25, (9), 1463-1469. (45)

Agarwal, R. K. P., J. Polyhedron 1991, 10, (23/24), 2809-2812.

(46) Bray, T. H.; Gorden, J. D.; Albrecht-Schmitt, T. E. J. Sol. State Chem. 2008, 181, (9), 2199-2204. (47) Chen, F.; Wang, C. Z.; Li, Z. J.; Lan, J. H.; Ji, Y. Q.; Chai, Z. F. Inorg. Chem. 2015, 54, (8), 3829-3834. (48) Falaise, C.; Charles, J. S.; Volkringer, C.; Loiseau, T. Inorg. Chem. 2015, 54, (5), 22352242. (49) Falaise, C.; Volkringer, C.; Vigier, J. F.; Henry, N.; Beaurain, A.; Loiseau, T. Chem. Eur. J. 2013, 19, (17), 5324-5331. (50)

Masci, B.; Thuéry, P. Cryst. Eng. Comm. 2008, 10, (8), 1082-1087.

(51)

Ok, K. M.; O'Hare, D. Dalton. Trans. 2008, (41), 5560-5562.

(52)

Thuéry, P. Eur. J. Inorg. Chem. 2013, 2013, (26), 4563-4573.

(53) Volkringer, C.; Mihalcea, I.; Vigier, J. F.; Beaurain, A.; Visseaux, M.; Loiseau, T. Inorg. Chem. 2011, 50, (23), 11865-11867. (54) Wu, H. Y.; Wang, R. X.; Yang, W.; Chen, J.; Sun, Z. M.; Li, J.; Zhang, H. Inorg. Chem. 2012, 51, (5), 3103-3107. (55) Ziegelgruber, K. L.; Knope, K. E.; Frisch, M.; Cahill, C. L. J. Sol. State Chem. 2008, 181, (2), 373-381. (56) Bai, Z.; Wang, Y.; Li, Y.; Liu, W.; Chen, L.; Sheng, D.; Diwu, J.; Chai, Z.; AlbrechtSchmitt, T. E.; Wang, S. Inorg. Chem. 2016, 6358–6360.


45


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 74

(57) Wang, Y.; Liu, Z.; Li, Y.; Bai, Z.; Liu, W.; Wang, Y.; Xu, X.; Xiao, C.; Sheng, D.; Diwu, J.; Su, J.; Chai, Z.; Albrecht-Schmitt, T. E.; Wang, S. J. Am. Chem. Soc. 2015, 137, (19), 61446147. (58)

Reger, D. L.; Leitner, A. P.; Smith, M. D. Cryst. Growth Des. 2016, 16, (1), 527-536.

(59) Adinarayana, K. N.; Sasidhar, P.; Balasubramaniyan, V. J. Environ. Radioactiv. 2013, 124, 93-100. (60)

Andrews, M. B.; Cahill, C. L. Chem. Rev. 2013, 113, (2), 1121-1136.

(61)

De Lill, D. T.; Gunning, N. S.; Cahill, C. L. Inorg. Chem. 2005, 44, (2), 258-266.

(62) Tribet, M.; Rolland, S.; Peuget, S.; Broudic, V.; Magnin, M.; Wiss, T.; Jégou, C. Proced. Mater. Sci. 2014, 7, 209-215. (63) Yudintsev, S. V.; Stefanovsky, S. V.; Nikonov, B. S.; Nikol’skii, M. S.; Livshits, T. S. Radiochemistry+ 2015, 57, (2), 187-199. (64) Zhang, J.; Zhang, F.; Lang, M.; Lu, F.; Lian, J.; Ewing, R. C. Acta Mater. 2013, 61, (11), 4191-4199. (65) Diwu, J.; Albrecht-Schmitt, T. E., Structural Chemistry of Trans Uranium Phosphonate In Metal phosphonate chemistry: from synthesis to applications, Clearfield, A.; Demadis, K., Eds. Royal Society of Chemistry: London, 2012; pp 607-631. (66)

Natrajan, L. S. Coord. Chem. Rev. 2012, 256, (15-16), 1583-1603.

(67)

Wang, K. X.; Chen, J. S. Acc. Chem. Res. 2011, 44, (7), 531-540.

(68)

Giesting, P. A.; Burns, P. C. Crystallogr. Rev. 2006, 12, (3), 205-255.

(69) Zhang, Y.; Karatchevtseva, I.; Bhadbhade, M.; Tran, T. T.; Aharonovich, I.; Fanna, D. J.; Shepherd, N. D.; Lu, K.; Li, F.; Lumpkin, G. R. J. Sol. State Chem. 2016, 234, 22-28. (70)

Thuéry, P. Cryst. Growth Des. 2009, 9, (2), 1208–1215.

(71) Wang, Y.; Li, Y.; Bai, Z.; Xiao, C.; Liu, Z.; Liu, W.; Chen, L.; He, W.; Diwu, J.; Chai, Z.; Wang, S.; Albrecht-Schmitt, T. E. Dalton. Trans. 2003, 44, (43), 18810-18814. (72)

Gorden, A. E.; Xu, J.; Raymond, K. N. Chem. Rev. 2003, 103, 4207-4282.

(73)

Van Horn, J. D.; Huang, H. Coord. Chem. Rev. 2006, 250, (7-8), 765-775.

(74) Zehnder, R. A.; Zeller, M., Lanthanide glutarate chlorides: Materials to access lanthanide coordination polymers with multiple organic ligands. In Southwest Regional Meeting of the American Chemical Society, ed.; Galveston, Texas, 2016. (75) Zehnder, R. A.; Zeller, M., Open frameworks assembling from selected f-elements and various di-carboxylic acids. In National Meeting of the American Chemical Society, ed.; San Diego, California, 2016.


46

Page 47 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(76) Blatov, V. A.; Shevchenko, A. P.; Proserpio, D. M. Cryst. Growth Des. 2014, 14, (7), 3576-3586. (77) O’Keeffe, M.; Peskov, M. V.; Ramsden, S. J.; Yaghi, M. Acc. Chem. Res. 2008, 41, (12), 1782-1789. (78) Alexandrov, E. V.; Blatov, V. A.; Kochetkov, A. V.; Proserpio, D. M. Cryst. Eng. Comm. 2011, 13, (12), 3947-3958. (79) Serezhkin, V. N.; Vologzhanina, A. V.; Serezhkina, L. B.; Smirnova, E. S.; Grachova, E. V.; Ostrova, P. V.; Antipin, M. Y. Acta. Cryst. B 2009, 65, (Pt 1), B45-B53. (80)

Krause, L.; Herbst-Irmer, R.; Sheldrick, G. M.; D., S. J. Appl. Cryst. 2015, 48, 3-10.

(81) Apex1 and Apex3, Saint, Sadabs In ed.; Bruker AXS Inc, Madison (WI), USA: 2013/2014. (82) Apex1 and Apex3, Saint, Sadabs In ed.; Bruker AXS Inc, Madison (WI), USA: 20132016. (83)

Sheldrick, G. M. Acta Cryst. 2015, C71, (Pt 1), 3-8.

(84) Hübschle, C. B.; Sheldrick, G. M.; Dittrich, B. J. Appl. Cryst. 2011, 44, (Pt 6), 12811284. (85)

Sheldrick, G. M. Acta. Cryst. 2008, A 64, (1), 112-122.

(86) Sheldrick, G. M., SHELXL2016. In ed.; University of Göttingen, Göttingen, Germany, 2016. (87)

Van der Sluis, P.; Spek, A. L. Acta Cryst. 1990, A46, 194-201.

(88) Zehnder, R. A.; Fontaine, N. C.; Zeller, M.; Renn, R. A. Acta Cryst. C 2010, 66, (12), m371-m374. (89)

Li, X.; Zha, M. Q.; Wang, X. W.; Cao, R. Inorg. Chim. Acta 2009, 362, 3357–3363.

(90)

Borkowski, L. A.; Cahill, C. L. Cryst. Growth Des. 2006, 6, (10), 2248-2259.

(91) Zou, R. Q.; Zhong, R. Q.; Du, M.; Pandey, D. S.; Xu, Q. Cryst. Growth Des. 2008, 8, (2), 452-459. (92)

Severance, R. C.; Smith, M. D.; zur Loye, H. C. Inorg. Chem. 2011, 50, (17), 7931-7933.

(93)

Batten, S. R.; Robson, R. Angew. Chem. Int. Ed. 1998, 37, 1460-1494.

(94)

Go, Y. B.; Wang, X.; Jacobson, A. J. Inorg . Chem. 2007, 46, 6594-6600.

(95)

Kim, J.-Y.; Norquist, A. J.; O'Hare, D. Dalton Trans. 2003, (14), 2813-2814.

(96) Serezhkina, L. B.; Grigor’ev, M. S.; Manakov, N. V.; Serezhkin, V. N. Radiochemistry+. 2015, 57, (5), 475–482.


47


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 48 of 74

(97) Benetollo, F.; Bombieri, G.; Herrero, J. A.; Rojas, R. M. J. Inorg. Nucl. Chem. 1979, 41, (2), 195-199. (98) Novikov, S. A.; Serezhkina, L. B.; Grigor’ev, M. S.; Manakov, N. V.; Serezhkin, V. N. Polyhedron 2016, 117, 644-651. (99)

Sahoo, B.; Patnaik, D. Nature 1960, 185, 683.

(100) Rao, G. G.; Rao, V. P.; Venkatamma, N. C. Z. Anal. Chem. Freseniu. 1956, 150, 178185. (101) Taylor, J. C. W., P. W. Acta Crystallogr. B. 1974, B30, (12), 2803-2805. (102) Lundgren, G. Ark. Kemi. 1953, 5, 349-363. (103) Mokry, L. M.; Dean, N. S.; Carrano, C. J. Angew. Chem. Int. Ed. 1996, 35, (13/14), 14971498. (104) Berthet, J. C.; Thuery, P.; Ephritikhine, M. Chem. Commun. 2005, 3415-3417. (105) Berthet, J. C.; Thuery, P.; Ephritikhine, M. Inorg. Chem. 2010, 49, (17), 8173-8177. (106) Knope, K. E.; Wilson, R. E.; Vasiliu, M.; Dixon, D. A.; Soderholm, L. Inorg. Chem. 2011, 50, (19), 9696-9704. (107) Nocton, G.; Pecaut, J.; Filinchuk, Y.; Mazzanti, M. Chem. Commun. 2010, 46, 27572759. (108) Takao, S.; Takao, K.; Kraus, W.; Emmerling, F.; Scheinost, A. C.; Bernhard, G.; Henning, C. Eur. J. Inorg. Chem. 2009, 4771–4775. (109) Qiu, J.; Burns, P. C. Chem. Rev. 2013, 113, (2), 1097-1120. (110) Falaise, C.; Volkringer, C.; Loiseau, T. Cryst. Growth Des. 2013, 13, (7), 3225-3231. (111) Mougel, V.; Biswas, B.; Pcaut, J.; Mazzanti, M. Chem. Commun. 2010, 46, 8648-8650. (112) Nocton, G.; Burdet, F.; Pecaut, J.; Mazzanti, M. Angew. Chem. Int. Ed. 2007, 46, (40), 7574-7578. (113) Knope, K. E.; Soderholm, L. Inorg. Chem. 2013, 52, (12), 6770-6772. (114) Zehnder, R. A.; Renn, R. A.; Pippin, E.; Zeller, M.; Wheeler, K. A.; Carr, J. A.; Fontaine, N.; McMullen, N. C. J. Molec. Struct. 2011, 985, (1), 109-119. (115) Zehnder, R. A.; Fontaine, N. C.; Mouawad, B. A.; Leonard, J. K.; Zeller, M.; Fronczek, F. R.; deLill, D. T.; Ballard, A.; Bonnette, D.; Head, A.; Ghimire, K.; Welch, J.; Barber, E. R.; Murray, J. M.; Dempsey, C.; Jenkins, J.; Jackson, G.; Tokunboh, M.; Bach, S. R.; Treadway Harris, J. A. Inorg. Chim. Acta 2017, in press, DOI: 10.1016/j.ica.2017.08.030.


48

Page 49 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(116) Wigenius, J. Conjugated Polyelectrolytes in Iinteractions with Biomolecules for Supramolecular Assembly and Sensing. Ph.D. Dissertation, Linköping University, Linköping, 2010.

SYNOPSIS We present the synthesis of various uranium open frameworks utilizing slow diffusion methods at room temperature. The structural properties and topologies of these materials are described and we illustrate that the glutarate linker assists in obtaining 3D networks, while the rather rigid terephthalate derivatives restrict the connectivity of the uranyl unit to form 1D and 2D underlying network systems.

U6O38-cluster with eight glutarate entities attached, For Table of Contents Use Only


49


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

177x27mm (300 x 300 DPI)


Page 50 of 74

Page 51 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


177x19mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

177x117mm (300 x 300 DPI)


Page 52 of 74

Page 53 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


76x104mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

101x86mm (300 x 300 DPI)


Page 54 of 74

Page 55 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


177x137mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

177x130mm (300 x 300 DPI)


Page 56 of 74

Page 57 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


88x68mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

88x68mm (300 x 300 DPI)


Page 58 of 74

Page 59 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


177x84mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

177x133mm (300 x 300 DPI)


Page 60 of 74

Page 61 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x83mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

177x71mm (300 x 300 DPI)


Page 62 of 74

Page 63 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x76mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x73mm (300 x 300 DPI)


Page 64 of 74

Page 65 of 74


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x54mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

88x87mm (300 x 300 DPI)


Page 66 of 74

Page 67 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


88x105mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x79mm (300 x 300 DPI)


Page 68 of 74

Page 69 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x99mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x89mm (300 x 300 DPI)


Page 70 of 74

Page 71 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x86mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

83x83mm (300 x 300 DPI)


Page 72 of 74

Page 73 of 74

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


83x75mm (300 x 300 DPI)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

43x44mm (300 x 300 DPI)


Page 74 of 74

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers

Recommend Documents