Large-Pore Layered Networks, Polycatenated Frameworks, and Three

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Large-pore Layered Networks, Polycatenated Frameworks and Three-dimensional Frameworks of Uranyl Tri(biphenyl)amine/ Tri(phenyl)amine Tricarboxylate: Solvent/Ligand-dependent Dual Regulation Shuai Wang, Lei Mei, Ji-pan Yu, Kong-qiu Hu, Zhi-rong Liu, Zhi-Fang Chai, and Wei-Qun Shi Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00246 • Publication Date (Web): 26 Jun 2018 Downloaded from http://pubs.acs.org on June 27, 2018

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Crystal Growth & Design

Large-pore Layered Networks, Polycatenated Frameworks and Three-dimensional Frameworks of Uranyl Tri(biphenyl)amine/Tri(phenyl)amine Tricarboxylate: Solvent/Ligand-dependent Dual Regulation Shuai Wang,†, ‡, ǁLei Mei, ‡,ǁ , Ji-pan Yu,‡, ǁ Kong-qiu Hu, ‡ Zhi-rong Liu*,† Zhi-fang Chai ‡,& and Wei-qun Shi*,‡ †

China School of Nuclear Science and Engineering, East China University of Technology,

Nanchang, 330013, China ‡

Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy

of Sciences, Beijing 100049,China &

School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of

Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou 215123, China

Keywords: Actinide • Uranyl-Organic Compound • Triphenylamine Tricarboxylate • Polycatenated Framework • Solvent-Dependent Regulation

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Abstract: In this work, we present the syntheses of four novel uranyl complexes of tri(biphenyl)amine tricarboxylate (L1) or triphenylamine tricarboxylate (L2), 1-4, with layerered networks or three-dimensional (3D) frameworks through solvothermal/hydrothermal reactions. Using

DMF

as

solvent,

compound

1

([NH2(CH3)2][UO2(L1)]·3DMF)

and

3

([NH2(CH3)2][UO2(L2)]·DMF) give nearly identical (6, 3)-connected large-pore layered networks in spite of slight difference in packing mode (‘ABC-ABC’ pattern in 1 vs ‘AB-AB’ pattern

in

3).

When

mixed

DMF/water

solvents

were

used,

compound

2

([NH2(CH3)2]2[UO2(L1)]2(NO3)2·H2O) with 2D + 2D → 3D polycatenated framework and compound 4 ([NH2(CH3)2][UO2(L2)]·2H2O) with (10, 3)-connected two-fold interpenetrating 3D framework were achieved from H3L1 and H3L2, respectively, which might be attributed to the induction of water molecules with strong hydrogen-bonding capacity. Most remarkably, the difference between 2D + 2D→3D polycatenated framework and (10, 3)-connected two-fold interpenetrating 3D framework demonstrates the vital role of conformation flexibility of ligand on the final structure of uranyl compounds, which should be related to the increased amount of phenyl groups of L1 ligand endowing its molecular skeleton more freedom and adjusting molecular conformation more easily. The physicochemical properties of them were also studied by powder X-ray diffraction, thermogravimetric analysis, IR spectroscopy, and luminescence spectra.


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INTRODUCTION As highly ordered inorganic-organic hybrid crystalline materials based on metal-ligand coordination bonds, metal-organic framworks (MOFs)1,

2

have undergone substantial

development during past decades for their promising applications in gas storage and separation,3, 4

catalysis,5-7 luminescence and sensing,8-11 and other fields12, 13 as well as their intriguing feature

of reticular syntheses, which means that the framework topologies, pore sizes and functionalities of MOFs can be properly regulated on demand. While functional MOFs with 3d-metal or 4fmetal centers as metal nodes occupy the mainstream of MOF-related arena, actinide ions featured by their 5f orbitals have been still less utilized in MOFs. Since last decade, actinidebearing hydrid materials14-19

have begun to arouse interests from inorganic chemists and

material specilists not only for their close relationship with nuclear fuel cycle by providing fundamental and sophisticated knowledge about actinides but also for great endeavor to direct functional hybrid materials with novel topologies and functions of interest. Following the same principles for guiding the synthesis of traditional MOFs, large conjugated polycarboxylate or multifurcated aromatic polycarboxylate ligands, which has been utilized substantially in synthesizing MOFs, are favored for the construction of actinide-based MOFs. For example, Wang et al20 explored the systheses of porous actinide-organic frameworks using 1,3,5-tri(4’-carboxylphenyl) benzoic acid,20,

21

3,5-di(4’-carboxylphenyl) benzoic acid,21 and

[1,1’-biphenyl]-3,4’,5-tricarboxylicacid22 with polyphenyl skeletons (Scheme 1a-c). Based on higly conjugated 4,4’,4’’,4’’’-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid, Farha et al23 designed and synthesized an anionic uranium-based MOF with ultra large pores enabling the efficient separation of organic dyes and biomolecules. Most strikingly, when starting from a simple unit, 5’-(4-carboxyphenyl)-2’,4’,6’-trimethyl-[1,1’:3’,1’’-terphenyl]-4,4’’-dicarboxylic acid, the same


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group24 achieved the bottom-up construction of a porous uranium-organic framework with the largest unit cell found to date for any nonbiological material. A recent work by Hong et al25 reported another non-interpenetrated anionic uranium-organic framework with tbo topology from tetrakis(4-carboxyphenyl)ethylene.

Besides

large

conjugated

polycarboxylate

ligands,

multifurcated non-conjugated but aromatic polycarboxylate ligands, which represent another important category of organic ligands for the fabrication of MOFs, have been also used to prepare actinide-organic frameworks, such as tris-(4-carboxylphenyl)phosphine oxide26,

27

or

(4,4’,4’’-(phenylsilanetriyl)tribenzoic acid.28 Recently, our group29 utilized an organic tetracarboxylic acid, tetrakis(4-carboxyphenyl)-methane and obtained two porous anionic uranylorganic frameworks featuring a highly symmetrical ctn or bor topology. The intriguing framework topologies and ultralarge pore sizes of actinide-based MOFs as demonstrated by previous studies impel us to explore more ligand systems for the cooordination assembly with actinide metal centers in persuit of novel possible coordniation patterns, topological structures and functions.30 Herein, a triphenylamine tricarboxylic acid derivative with elongated biphenyl skeletons, (4',4''',4'''''-nitrilotris([1,1'-biphenyl]-4-carboxylic acid) (H3L1), was synthesized and firstly employed to synthesize uranium-based MOFs. And meanwhile, the simple triphenylamine tricarboxylic acid with short arms, 4,4',4''-nitrilotribenzoic acid (H3L2), which has been previously used for building thorium-organic layered and framework structures, was also used as a control compound of H3L1 (Scheme 1j-k).


4

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Scheme 1. Molecular structures of large conjugated or multifurcated aromatic polycarboxylate ligands used for constructing actinide-organic frameworks in previous reports (a-i) and in this work (j: H3L1, 4',4''',4'''''nitrilotris([1,1'-biphenyl]-4-carboxylic acid with arm length of 10.59 Å); k: H3L2, 4,4',4''-nitrilotribenzoic acid with arm length of 6.30 Å).

In this work, we report four novel uranyl complexes of tri(biphenyl)amine tricarboxylate or triphenylamine tricarboxylate, 1-4, with layerered networks, polycatenated frameworks or threedimensional (3D) frameworks through solvothermal/hydrothermal reactions of H3L1 and H3L2 with uranyl (Figure 1). The most intriguing is the template-free formation polycatenated


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framework found in compound 2, which is just enabled by the ultra-large honeycomb-like pores of two-dimensional (2D) layered networks based on elongated triphenylamine tricarboxylate linkers, and the ultra-large loops facilitate a high degree of polycatenation with three sets of 2D grids passing across one flat 2D grid along a different direction. Moreover, structural variance from 1-4 can be achieved through not only diverse ligands but only different solvent systems. The reasons for this interesting phenomenon is also discussed in detail.

Figure 1. Layerered networks (a and c) or three-dimensional frameworks (b and d) through

solvothermal/hydrothermal reactions of H3L1 and H3L2 with uranyl. Different colors (a: green, blue and orange; b: green, light green, blue and light blue; c: green and blue; d: green and blue) in all the diagrams denote different sets of layered networks or frameworks.


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EXPERIMENTAL SECTION Materials and Methods. Caution! Uranium is an element of radioactive chemical toxicity that requires

strict

precautions

during

the

operation

of

the

experiment.

The

Tris(4’-

carboxybiphenyl)amine (H3L1)31 and tricarboxyltriphenylamine (H3L2)32 were synthesized as previously. Other reagents and materials are used in the synthesis: UO2(NO3)2·6H2O (Sinopharm Chemical Reagent, 99%), trifluoroacetic acid (Energy Chemcial, 99%), N,N-Dimethylformamide (DMF, Xilong Chemical, 98%), and ultrapure water (18.2 MΩ·cm−1). The stock solutions of UO2(NO3)2·6H2O (0.5 M) was prepared prior to the synthesis procedure. In the experiment, powder X-ray diffraction (PXRD, Bruker, D8-Advance X-ray Diffractometer) was performed with Cu Kα radiation (λ = 1.54084 Å). Fluorescence spectra of the sample were measured on the Hitachi F-4600 fluorescence spectrophotometer with an excited wavelength at 420 nm. The photomultiplier tube voltage was 700 V, the excitation and the emission slit width were 5.0 and 5.0 nm, respectively, and the scan speed was 60 nm·min−1. FTIR measurement was obtained on a Bruker Tensor 27 infrared spectrometer. Sample was diluted with spectroscopic KBr and pressed into a pellet. The measured wavenumber is distributed from 400 to 4000 cm-1. Thermogravimetric analysis (TGA, TA Instruments, Q600) was employed in air atmosphere with a heating rate of 5 °C·min−1. Synthesis. All the uranyl CPs were solvothermally or hydrothermally synthesized under autogenous pressure adopting 15 mL Teflon-lined Parr-type autoclaves. [NH2(CH3)2][UO2(L1)]·3DMF (1). 0.5M aqueous solution of UO2(NO3)2·6H2O (0.08 ml, 0.04 mmol), H3L1 (24.2 mg, 0.03 mmol), trifluoroacetic acid (0.06 ml, 0.81 mmol), DMF (2.0 mL) were loaded to a 15 mL autoclave. The autoclaves were sealed and heated to 100 °C in an


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oven for 2 days, then cooled to room temperature passively. Brown-yellow prism-like microcrystals were produced, which were then filtered off, rinsed with DMF, and subjected to air-drying at room temperature. Yield: 16.8 mg (51.3% based on uranium). [NH2(CH3)2]2[UO2(L1)]2(NO3)2·H2O (2). 0.5M aqueous solution of UO2(NO3)2·6H2O (0.08 ml, 0.04 mmol), H3L1 (24.2 mg, 0.03 mmol), trifluoroacetic acid (0.08 ml, 1.08 mmol), DMF (1.5 mL) and ultrapure water (0.5 ml) were loaded to a 15 mL autoclave. The autoclaves were sealed and heated to 100 °C in an oven for 2 days, then cooled to room temperature passively. Accompanied by a considerable amount of 1 in brown-yellow color, luminous yellow crystals of 2 were produced, which were then filtered off, rinsed with DMF and ultrapure water, and subjected to air-drying at room temperature. [NH2(CH3)2][UO2(L2)]·DMF (3). 0.5M aqueous solution of UO2(NO3)2·6H2O (0.08 ml, 0.04 mmol), H3L2 (11.31 mg, 0.03 mmol), trifluoroacetic acid (0.08 ml, 1.08 mmol), DMF (2.0 mL) were added to a 15 mL autoclave. The autoclaves were sealed and heated to 120 °C in an oven for 3 days, then cooled to room temperature naturally. Yellow crystals in a shape of hexagonal prism were produced in a very low yield, which were then filtered off, rinsed with DMF, and subjected to air-drying at room temperature. [NH2(CH3)2][UO2(L2)]·2H2O (4). UO2(NO3)2·6H2O (0.50 M, 0.08 mL), H3L2 (11.31 mg, 0.03 mmol), trifluoroacetic acid (0.08 ml, 1.08 mmol), DMF (1.5 mL) and ultrapure water (0.5 ml) were loaded to a 15 mL autoclave. The autoclaves were sealed and heated to 120 °C in an oven for 3 days, then cooledto room temperature naturally. Dark-yellow crystals were produced, then filtered off, washed with DMF and ultrapure water, and subjected to air-drying at room temperature. Yield: 8.4 mg (42.9% based on uranium).


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Table 1. Crystal data and structure refinement for uranyl compounds 1-4. 1

2

3

4

Formula

C39H24NO8U

C80H48N5O23U2

C21H12NO8U

C21H12NO8U

Formula weight

872.62

1923.29

644.35

644.35

Crystal system

trigonal

monoclinic

trigonal

orthorhombic

Space group

P3212

C2/c

P-31c

Fddd

a, Å

22.2597(16)

42.132(6)

14.7342(7)

b, Å

22.2597(16)

11.9656(17)

14.7342(7)

8.3019(4) 27.9965(13)

c, Å

10.7536(10)

18.373(2)

8.5641(5)

51.493(3)

α, deg

90

90

90

90

β, deg

90

113.369(3)

90

90

γ, deg

120

90

120

90

4614.5(8)

8503(2)

1610.1(2)

11968.2(1)

Z

3

4

2

16

T, K

293(2)

294(2)

295(2)

295(2)

V, Å

3

1263.0

3724.0

602.0

4816.0

3

Dc, g/cm

0.942

1.502

1.329

1.430

-1

µ (mm )

7.680

3.876

5.071

15.575

Rint

0.1137

0.0988

0.0246

0.0488

R1,wR2(I>=2σ(I))

0.0949, 0.2256

0.0594, 0.1334

0.0623, 0.1711

0.0655, 0.1422

R1,wR2 (all data)

0.1873, 0.2704

0.0787, 0.1418

0.0669, 0.1775

0.0592, 0.1402

F(000)

X-ray Single Crystal Structure Determination. X-ray diffraction data of compounds 1 and 4 were collected on a Bruker APEXII X-ray diffractometer equipped with a CMOS PHOTON 100 detector with a Cu Kα X-ray source (Kα = =1.54178 Å), and the data of 2 and 3 was on the same diffractometer using a Mo Kα X-ray source (Kα = 0.71073 Å). All data was integrated using the SAINT software package, and an absorption correction was applied using SADABS. Using Olex2,33 all crystal structures were solved by means of direct methods (SHELXS-9734) and refined with full-matrix least squares on SHELXL-2014.34,

35

The aromatic and hydroxyl

hydrogen atoms were placed in calculated, ideal positions and refined as riding on their respective carbon or oxygen atoms. RIGU and DFIX were used to create a chemically sensible


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model for 1, 2 and 4, and ISOR were used to constrain the displacement parameters for 1, 2 and 3. PLATON/SQUEEZE36 was used for 4 to afford a neo-site diffraction intensities of solvent water molecules. It should be mentioned that, since poor diffraction capability of large pores of two-dimensional networks, the crystal data of 1 and 2 can only afford relatively low resolution and/or relatively high R values. The crystal data of these four compounds are given in Table 1. Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-1818442 (1), CCDC1818443 (2), CCDC-1818444 (3), CCDC-1818445 (4).

RESULTS AND DISCUSSION Crystal structures. Compound 1 was synthesized solvothermally from uranyl nitrate and H3L1 in DMF in the presence of trifluoroacetic acid. The triangular-prism shaped crystals (Figure S1a) crystallize in the P3212 space group of trigonal crystal system, and have only half of one eightfold coordinated monouranyl center as well as half of a L1 ligand molecule in its asymmetric unit (Figure 2a-b). Each uranyl in a hexagonal bipyramid geometry is coordinated by three η2carboxylic groups from different L1 ligands with equatorial U-O distances from 2.47(2) Å (U1O2) to 2.49(3) Å (U1-O5) (Table S1), and connected by these tritopic L1 linkers to form a honeycomb-like layered 2D network without any warp (Figure 2b-c). A hexagonal loop consisting of three uranyl units and three 2/3 entries of L1 linkers (two out of three arms of tritopic L1) is the basic unit of this honeycomb-like layered 2D network, of which the maximum distance between the vertices is 25.74 Å and the distance between the parallel edges is 22.26 Å, both of which are consistent with the ultralong edges of hexagonal loops (12.82 Å, 12.87 Å and 12.87 Å, Figure 3a). Interestingly, the layered networks pack in triplets (namely as ‘ABC-


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ABC‘ pattern) with all the uranyl centers aligned in a staggered mode (Figure 2d-e). All the adjacent layers give the same interlayer spacing of ~3.58 Å (Figure 3a).

Figure 2. a) The asymmetric unit of compound 1; b) (6, 3)-connected 2D layered network with ultra-large honeycomb-like loops in 1. Insert: eight-fold coordinated coordination sphere (axial: O4; equatorial: O2, O3, O5) of uranyl center; c) Side-on view of 2D flat layered network analogous to a straight line without any warp in 1; d) Crystal packing of 2D layered networks viewed from c axis in 1 (different colors corresponding to different sets of 2D layered networks); e) Crystal packing of 2D layered networks viewed from b axis in 1 showing its packing mode in triplets namely as ‘ABC-ABC‘ (different colors corresponding to different sets of 2D layered networks).


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Figure 3. Tritopic linker-derived minimum loops in 1-4 and the corresponding final topological diagrams (U and N atoms are set as linkage nodes, and the data shown as edge lengths are corresponding to distances between adjacent U and N atoms): a) 1 with (6, 3)-connected topology and layer-by-layer crystal packing; b) 2 with (6, 3)-connected topology and final polycatenated framework; c) 3 with (6, 3)-connected topology and layer-by-layer crystal packing ; d) 4 with (10, 3)-connected topology and two-fold interpenetrating framework.


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When a mixed solvent system of DMF/H2O (3/1, v/v ) was used instead of pure DMF for the reaction of uranyl nitrate and H3L1, compound 2, that is luminous yellow block crystal, was obtained as accompanying product of 1 (Figure S1b). The crystal of 2 crystallizes in the C2/c space group of monoclinic crystal system, indicating a lower crystallographic symmetry than that of 1. A full set of L1 molecule and one uranyl center as well as small charged counter-ions are present in its asymmetric unit (Figure 4a). In spite of lower symmetry of 2, the coordination modes of uranyl and L1 and even the honeycomb-like layered 2D network here are totally identical to those found in 1. Certainly, there are still little difference between 1 and 2, for instance, the side-on view of honeycomb-like layered 2D network shows that it is no longer a flat plane but has a slight bending (Figure 4c). Correspondingly, hexagonal loops of the layered 2D network also reveals to be slightly distorted (Figure 4b). What is more unusual is final topological structure of 2, which is not just layer-by-layer packing, but a 2D + 2D → 3D polycatenated framework with higher complexity (Figure 4d-e). It is no doubt that the additional solvent atmosphere of water plays a vital role in inducing the formation of polycatenated framework of 2, and the slight distortion of honeycomb-like layered 2D networks might enable this intriguing assembly feasible. Interestingly, parallel networks along one direction are spatially arranged in groups of two with an interlayer spacing of 3.61 Å and inter-group spacing of 6.42 Å (Figure 3a), which pass through large hexagonal loops of the other inclined subsets. This type of polycatenated framework is very similar to several previously-reported structures,21, 37-42

especially those based on terephthalate41 or biphenyl dicarboxylate38 linker. Another two

important compositions in 2 are free dimethylammonium ([NH2(CH3)2]+) cations and nitrate (NO3-) anions located at the quadrilateral channels with both side lengths of 6.42 Å (Figure S2ab). Detailed analysis reveals that the [NH2(CH3)2]+ cations seem to link differently oriented


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uranyl-organic networks by wide-spread weak interactions (C([NH2(CH3)2]+)---O(carboxyl): 3.54 Å and 3.64 Å, Figure S2c) between [NH2(CH3)2]+ cations and adjacent uranyl centers and finally achieve the formation of polycatenated frameworks of 2. It is worth noting that, 41, 43-45 unlike those 2D + 2D→3D polycatenated frameworks always needing bulky templating agents, the polycatenated framework found here is formed without any extraneous templates. It might be related to improved rigidity of the tri(biphenyl)amine skeleton, which has something in common with the cases of 2D + 2D + 2D →3D polycatenation with three different sets of independent networks from three directions without templates invovled.21, 37 Moreover, due to a moderate ring size, the number of inclined networks that each hexagonal loop can accommodate to pass through itself is a total of three here (Figure 5), which is larger than that for uranyl-terephthalate systems (a total of two),41 but smaller than that for uranyl-biphenyldicarboxylate system (a total of four).38


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Figure 4. a) The asymmetric unit of compound 2; b) (6, 3)-connected 2D layered network with ultra-large honeycomb-like loops in 2. Insert: eight-fold coordinated coordination sphere (axial: O3, O4; equatorial: O1, O2, O5 , O6, O7 and O8) of uranyl center; c) Side-on view of 2D flat layered network analogous to a straight line with slight warp in 2; d) polycatenated framework in which parallel networks along one direction in groups of two (different colors corresponding to different sets of 2D layered networks) pass through large hexagonal loops of the other inclined subsets (in blue color) in 2; e) total topological view of polycatenated framework of 2 (different colors corresponding to different sets of 2D layered networks).


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Figure 5. The total number of inclined networks that each hexagonal loop can accommodate to pass through itself dependent on the size of minimum hexagonal loop: a) two sets for uranyl-terephthalate; b) three sets of uranyl-L1 in this work; c) four sets of uranyl biphenyldicarboxylate.

Compound 3 was synthesized solvothermally from uranyl nitrate and H3L2 with a shorter arm-length in DMF in the presence of trifluoroacetic acid. The hexagonal prism shaped crystals (Figure S1c) crystallize in the high-symmetric P-31c space group of trigonal crystal system, and U and N atoms are both located at the C3 axis (Figure 6a). Each uranyl in a hexagonal bipyramid geometry is coordinated by three η2-carboxylic groups from different L2 ligands with equatorial U-O distance of 2.447(10) Å (U1-O2) (Table S1), and connected by these tritopic L2 linkers to form a honeycomb-like layered 2D network without any warp (Figure 6b-c). A hexagonal loop consisting of three uranyl units and three 2/3 entries of L2 linkers (two out of three arms of


16

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tritopic L2) is the basic unit of this honeycomb-like layered 2D network, of which the maximum distance between the vertices is 17.01 Å and the distance between the parallel edges is 14.73 Å, both of which are consistent with the edges of orthhexagonal loops (8.51 Å, 8.51 Å and 8.51 Å, Figure 2c). Remarkably, the layered networks pack in couple (namely as ‘AB-AB‘ pattern) with all the amine-nitrogen atoms are stacked face-to-face excactly but the uranyl centers aligned in a staggered mode with a deflection angle of 60° (Figure 6d-f). All the adjacent layers give the same interlayer spacing of ~4.28 Å (Figure 3c).

Figure 6. a) The asymmetric unit of compound 3; b) (6, 3)-connected 2D layered network with

ultra-large honeycomb-like loops in 3. Insert: eight-fold coordinated coordination sphere (axial:


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O1; quatorial: O2) of uranyl center; c) Side-on view of 2D flat layered network analogous to a

straight line without any warp in 3; d) Crystal packing of 2D layered networks viewed from c axis in 3 (different colors corresponding to different sets of 2D layered networks); e) Crystal packing of 2D layered networks viewed from b axis in 3 showing its packing mode in triplets namely as ‘AB-AB‘ (different colors corresponding to different sets of 2D layered networks). Similar to the cases for 1 and 2, another new uranyl compound 4, was obtained as accompanying product of 3 (Figure S1d), when a mixed solvent system of DMF/H2O (3/1, v/v ) was used instead of pure DMF for the reaction of uranyl nitrate and H3L2. The crystal of 4 crystallizes in the Fddd space group of orthorhombic crystal system, and have only half of one eight-fold coordinated monouranyl center and as well as half of a L2 ligand molecule in its asymmetric unit (Figure 7a). Each uranyl in a hexagonal bipyramid geometry is coordinated by three η2-carboxylic groups from different L2 ligands with equatorial U-O distances from 2.444(7) Å (U1-O4) to 2.471(7) Å (U1-O2) (Table S1). It is interesting to find that, the tritopic L2 linkers undergo remarkable changes from a nearly flat conformation to a distorted non-coplanar conformation (Figure 7b-c and Figure S3), and results in a 3D framework with a (10, 3)connected topology (Figure 7d-e), not a (6, 3)-connected layered network any more. Although hexagonal rings can still be seen viewed from a axis, they are not still real planar hexagon, but a helical chain along a axis (Figure S3). Moreover, the 3D framwork can further assemble with each other to finally form a two-fold interpenetrating structure (Figure 5f-g).


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Figure 7. a) The asymmetric unit of compound 4; b) (10, 3)-connected topology and two-fold interpenetrating framework in 4. Insert: eight-fold coordinated coordination sphere (axial: O1; quatorial: O2, O3, O4) of uranyl center; c) Side-on view of 3D networks analogous to a fork in 4; d) Crystal packing of 3D networks viewed from a axis in 4; e) Crystal packing of 3D networks viewed from a axis in 4; f) Crystal packing of 3D two-fold interpenetrating networks (different colors corresponding to different sets of 3D networks)viewed from b axis in 4; g) Crystal packing of 3D two-fold interpenetrating networks (different colors corresponding to different sets of 3D networks) viewed from b axis in 4;

Solvent-dependent and ligand-dependent Regulation. Since the hydrophobic property of L1 and L2, the syntheses for all these four compounds were performed through solvothermal


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reactions in the presence of DMF (pure DMF or DMF-H2O mixed solvent). Besides, in order to control the basicity of solvothermal system, different types of acids including nitric acid, chloroacetic acid, or trifluoroacetic acid were used during the synthesis of the crystals, and only the trifluoracetic acid with moderate acidity gave crystals suitable for single-crystal determination. The most crucial factor affecting the solvothermal outcomes is the solvent used, for which the presence of certain amount of water or not plays an important role. For both uranyl compound series with L1 or L2 ligands, solvent-dependent structural regulation is observed. When pure DMF was used in the solvothermal reaction, only 2D layered networks were obtained for either L1 or L2 ligand. However, the addition of water in the solvent system, both solvothermal/hydrothermal reactions of L1 or L2 with uranyl afford totally different uranyl compound. Detailed structural analysis of 1-4 indicates that three adjacent uranyl centers connected to one L1/L2 linker in the uranyl compounds (2 and 4) from solvent system containing water undergo different deflection from the former plane of uranyl compounds from pure DMF solvent (1 and 3) (Figure 8). Obviously, the deflection trend is achieved through the rotation of phenyl moiety around C-C bond axis in L1 and L2, which might be attributed to the induction of water molecules with strong hydrogen-bonding capacity. For instance, this induction of water-based hydrogen bonds is clearly confirmed by the locations of crystal-lattice water molecules (O2W) near phenyl moieties in 4 (Figure S4b-c). Moreover, it is found that the crystal-lattice water molecules (O1W) promote the formation and stabilization of two-fold interpenetrating networks through hydrogen-bonding to terminal oxygen atoms of uranyl centers from adjacent helical chains of 4.


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Figure 8. Solvent-dependent regulation of uranyl compounds from H3L1 and H3L2. The plates in different colors (green, purple and blue) refer to the equatorial planes of three uranyl centers around one L1 or L2 ligand. Left diagrams: 1 (top) and 2 (bottom); Left diagrams: 3 (top) and 4 (bottom). Another important issue is the difference of uranyl compounds based on L1 and L2, even in the same solvent system. For example, compounds from DMF (1 and 3) show slight difference in packing mode (‘ABC-ABC’ pattern in 1 vs ‘AB-AB’ pattern in 3) in spite of nearly identical layered networks, and compounds from DMF/water (2 and 4) are totally different in structures (2D + 2D→3D polycatenated framework in 2 vs (10, 3)-connected two-fold interpenetrating 3D framework in 4, see Figure 9). Again, the disparity in total topologic structure should be also assigned to different molecular flexibility of L1 and L2. Considering the significant difference


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between 2 and 4, we make a detailed comparison between them. As shown in Figure 8, although both the uranyl moieties undergo obvious deflections in 2 and 4, degree of deviation is not the same. Although three uranyl equatorial planes are not coplanar in 2, all of them remain in parallel, ensuring the formation of final uneven but still layered network (Figure 8, bottom of left diagrams). However, only two uranyl equatorial planes are still in parallel and anther one is skewed with an inclination angle of 45.8°, promoting the formation of (10, 3)-connected 3D framework with structural unit of helical chain (Figure 8, bottom of right diagrams). Thinking from the vital role of conformation flexibility of ligand on the final structure of uranyl compounds, we can hypothesize that the increased amount of phenyl groups of L1 ligand endows its molecular skeleton more freedom than L2 with shorter arm-length, and enables it adjust molecular conformation easily. Hence, even displacement in a more or less extent occurs for one phenyl moiety, the total regularity of molecular structure can be retained through the structural adjustment from the other groups (phenyl or carboxyl). Nevertheless, the selfadjustment of L1 with shorter arm-length is indeed not good as L2. Therefore, compound 2 keep its basic structural unit of layered network and finally assemble into 2D + 2D→3D polycatenated framework, whist compound 4 results in a (10, 3)-connected 3D framework with two-fold interpenetrating crystal-packing.


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Figure 9. a) 2D + 2D→3D polycatenated framework in 2 with large hexagons (blue) passing

through by three sets of 2D networks; b) (10, 3)-connected two-fold interpenetrating 3D framework in 4.

Thermogravimetric analysis, IR Spectroscopy and Luminescence Spectra Powder X-ray diffraction patterns for 1, 3, and 4 (Figure S5-7) agree well with the simulated ones based on the single-crystal structures, indicating their high phase purity. It is worth noting that differences in peak intensity between simulated and experimental patterns should be attributed to enhanced intensity of parts of certain crystal orientation. Therefore, characterization of 1, 3, and 4 by IR Spectroscopy, thermogravimetric analysis and luminescence spectra were performed, whilst

compound 2 were excluded out to the further characterizations for the

unavailability of sample in pure phase.


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Thermal stability of 1, 3, 4 was studies by a thermogravimetric (TGA) measurement within the temperature range of 25-800°C (Figure S11-13). All the three compounds undergo the loss of solvent molecules (DMF and/or H2O) in crystal lattice before 310 °C, followed by collapse of the framework starting at 310-320°C and ending at 466-484 °C. Specifically, for compound 1, a significant amount of weight loss observed in the range of 60-180 °C should be attributed to the loss of DMF solvent and dimethyl ammonium in the crystal lattice (observed: 74.5%, calculated: 74.1%). The decomposition of molecular framework in 1 is observed during the temperature of 320-466 °C, and finally affords a U3O8 black powder giving a residual weight of 24.2%, which is close to the expected value (23.8%). Compound 3 shows a similar decomposition process though the weight loss temperatures are slightly different. For 3, the first weight loss process corresponding to the loss of DMF solvent and dimethyl ammonium (observed: 83.3%, calculated: 82.9%) and the second process corresponding to framework decomposition (observed: 36.3 %, calculated: 36.0 %) starts at ~90 °C and ~310 °C, respectively. Unlike 1 and 3, compound 4 containing lattice water molecules shows two separated fractions of weight loss before framework decomposition: the first one among the range of 85-193 °C might be the loss of water molecules (observed: 94.7%, calculated: 95.0%); the other among the range of 242-310 °C is dimethyl ammonium in the crystal lattice (observed: 87.9%, calculated: 88.7%). After a sharp weight decrease in the range of 320-484°C corresponding to thermolysis of framework, the remaining weight losses observed in 4 are close to the calculated values (observed: 38.6%, calculated: 38.7%). In the IR spectra of 1, 3, and 4 (Figure S8-10), the strong vibration absorption peaks at 16601670 cm–1 is assigned to the asymmetric stretching vibrations of carboxylate group (1: ~1664 cm–1; 3: ~1660 cm–1, 4: ~1660 cm–1) . As expected, the uranyl vibration absorption peaks for 1, 3,


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and 4 occur at 916 cm–1, 918 cm–1, 912 cm–1, respectively. All these results are in consistent with the single-crystal structural analyses. In terms of luminescence spectra, although solid-state emission spectra of 1, 3, and 4 were investigated at room temperature with an excited wavelength at 420 nm, nearly complete quenching of uranyl emission is observed for all of them, which might be related with energy transfer between urany center and high-conjugated tri(biphenyl)amine or triphenylamine backbones.

CONCLUSIONS In this work, we present the syntheses of four novel uranyl complexes of tri(biphenyl)amine tricarboxylate or triphenylamine tricarboxylate, 1-4, with layerered networks or threedimensional (3D) frameworks through solvothermal/hydrothermal reactions. Remarkably, the structural change from layerered networks to 3D framework after adding water solvent suggests solvent-dependent regulation, which might be attributed to the induction of water molecules with strong hydrogen-bonding capacity, and the difference between 2D + 2D→3D polycatenated framework and (10, 3)-connected two-fold interpenetrating 3D framework demonstrates the vital role of conformation flexibility of ligand on the final structure of uranyl compounds, which might be related to the increased amount of phenyl groups of L1 ligand endowing its molecular skeleton more freedom and adjusting molecular conformation more easily. The work here enriches the library of uranyl-organic compounds with functional linkers, and most importantly, provides valuable insight into the solvent/ligand dependent regulation mechanism of uranylorganic compounds, which will be helpful to the preparation of new functional uranyl-organic compounds in future.


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ASSOCIATED CONTENT Supporting Information Several typical figures, tables and related characterization including powder X-ray diffraction, IR

spectroscopy, luminescence spectra, and thermogravimetric analysis are included in the Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected]; [email protected] Notes The authors declare no competing financial interests. Author Contributions ǁ

These authors contributed equally.

ACKNOWLEDGMENT We thank the support of this work by the Science Challenge Project (JCKY2016212A504), the National Natural Science Foundation of China (21577144 and 21671191) and the Major Resarch Plan “Breeding and Transmutation of Nuclear Fuel in Advanced Nuclear Fission Energy System” of the Natural Science Foundation of China (91426302 and 91326202).

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"For Table of Contents Use Only"

Large-pore Layered Networks, Polycatenated Frameworks and Three-dimensional Frameworks of Uranyl Tri(biphenyl)amine/Tri(phenyl)amine Tricarboxylate: Solvent/Ligand-dependent Dual Regulation Shuai Wang,†, ‡, ǁLei Mei,

‡,ǁ

, Ji-pan Yu,‡, ǁ Kong-qiu Hu, ‡ Zhi-rong Liu*,† Zhi-fang Chai

‡,&

and Wei-qun

,‡

Shi*

Synopsis： Uranyl tri(biphenyl)amine/tri(phenyl)amine tricarboxylate compounds with nearly identical (6, 3)-connected large-pore layered networks in spite of slight difference in packing mode (‘ABCABC’ pattern in 1 vs ‘AB-AB’ pattern in 3) were synthesized using DMF as solvent, while a 2D + 2D → 3D polycatenated framework and a (10, 3)-connected two-fold interpenetrating 3D framework were achieved in mixed DMF/water solvents from H3L1 and H3L2, respectively.


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Large-Pore Layered Networks, Polycatenated Frameworks, and Three

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