Two Novel Self-Catenated MetalâOrganic Frameworks with Large

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Two Novel Self-Catenated Metal-Organic Frameworks with Large Accessible Channels Obtained by Mixed-Ligand Strategy: Adsorption of Dichromate and Ln3+-Post Synthetic Modification Yingying Sun, Ruidan Ma, Fengyuan Wang, Xianmin Guo, Shaowen Sun, Huadong Guo, and Eugeny V. Alexandrov Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00657 • Publication Date (Web): 25 Jul 2019 Downloaded from pubs.acs.org on July 29, 2019

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Crystal Growth & Design

Two Novel Self-Catenated Metal-Organic Frameworks with Large Accessible Channels Obtained by Mixed-Ligand Strategy: Adsorption of Dichromate and Ln3+-Post Synthetic Modification Yingying Sun,† Ruidan Ma,† Fengyuan Wang,† Xianmin Guo,*,† Shaowen Sun,† Huadong Guo,*,† and Eugeny V. Alexandrov *,‡§ †Department

of Chemistry, Changchun Normal University, Changchun 130032, People’s Republic of China

‡Samara

State Technical University, Molodogvardeyskaya St. 244, Samara 443100, Russia

§Samara

Center for Theoretical Material Science (SCTMS), Samara University, Moskovskoe shosse 34, 443086 Samara, Russia

ABSTRACT

ACS Paragon Plus Environment

1

Crystal Growth & Design 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

Two

novel

metal-organic

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frameworks,

namely

[Cd3(bdc)(HCOO)2(tipo)2(H2O)2]·2NO3·6DMF (1) and [Zn8(OH)4(bpdc)6(tipo)4]·16DMF (2)

(tipo=

tris[4-(1H-imidazol-1-yl)phenyl]phosphine

oxide,

H2bdc=

phenyl-1,4-

dicarboxylic acid, H2bpdc=biphenyl-4,4'-dicarboxylic acid) have been successfully synthesized. Compound 1 exhibits a cationic 4,6-connected self-catenated framework with large 1D channels. Compound 2 features a 3,4-connected self-catenated framework with potential O-donor located on the surface of the channels. Compound 1 shows a high adsorption for dichromate. Post synthetic modification of 2 by lanthanide ions (Eu3+ and Tb3+) afforded fluorescent materials.

INTRODUCTION In the last decades, metal-organic frameworks (MOFs) have received great attention due to their wide structural diversity1-6 and promising application in adsorption, catalysis, luminescence, sensing, biomedicine, energy conversion, electronics, etc.7-12 As an emerging class of porous host materials, MOFs enrich versatile host-guest systems.1317

The pore size and surface area of MOFs can be finely tuned by rational selection of

metal ions and design of organic ligands.18-20 The adsorption capacity of MOFs to the guests or the stability of host-guest functional materials mainly depends on the interactions between the frameworks and guest molecules in MOFs’ channels, including hydrogen bonds, π···π stacking interactions, electrostatic forces and coordination


2

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bonds.21-26 The adsorption of guests into the porous framework depends on the number and strength of host-guest interactions, and one of the effective strategies to increase them is constructing charged microporous MOFs. Thus, ions of inorganic molecules and organic dyes permeant to the pores can interact stronger with the frameworks of opposite charge.27-30 Furthermore metal ions can be strongly coordinated on the pore surface to give a new post-synthetically modified MOF with improved properties such as tunable luminescence in the case of lanthanide cations.31-33 O

OH

N N

O

N

OH

N

O P

HO

O

H2bdc

N HO

O

H2bpdc

N

tipo

Scheme 1. The ligands used in synthesis of the two MOFs In this work, we synthesized a new tripodal ligand, tris[4-(1H-imidazol-1yl)]phosphine oxide (tipo) as the building unit (Scheme 1). Similar to N-centered analogues, such a ligand of triangular shape, medium flexibility and long spacing can give highly porous and robust frameworks.34-37 However, the same construction features are also beneficial for entangled motifs, and combinations of porosity and entanglements are really rare cases.38-41 Moreover, the P=O group can coordinate a metal ion to expand the network connectivity or to provide a potential adsorption site.


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Successfully, the mixed-ligand strategy resulted in two MOFs with unusual patterns of self-catenation,

namely

[Cd3(bdc)(HCOO)2(tipo)2(H2O)2]·2NO3·6DMF

(1)

and

[Zn8(OH)4(bpdc)6(tipo)4]·16DMF (2). Compound 1 is stable in water and shows highly efficient Cr2O72- removal from aqueous solution for the cationic framework properties. Post-synthetic modification of 2 with Eu3+ and Tb3+ afforded fluorescent lanthanide(III)loaded materials.

EXPERIMENTAL SECTION Materials and instrumentation The ligand tipo was synthesized according to our reported method.42 All the other starting materials were of analytic grade and used as received without further purification. IR spectra were obtained from KBr pellets on a Perkin-Elmer 580B IR spectrometer in the 400-4000 cm-1 region. TGA was performed on a Perkin-Elmer TG-7 analyzer heated from 30 to 800 °C under nitrogen (Fig. S5). The luminescent properties of these compounds were measured on a HITACHI F7000 spectrometer. Powder X-ray diffraction (PXRD) data were recorded on a Bruker D2 Phaser. UV-vis adsorption spectra were collected on a Shimadzu UV-3101PC spectrophotometer to monitor the ion-exchange progress. Synthesis of 1


4

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A mixture of Cd(NO3)2·4H2O (0.0616g, 0.2mmol), tipo (0.0476g, 0.1mmol), H2bdc (0.0166g, 0.1mmol), DMF (8ml), methanol (1ml) and HNO3 (1ml, 0.5M) was placed in a Teflon reactor (20ml) and heated at 80°C for 2 days and then cooled to room temperature. The colorless crystals were washed with ethanol and air-dried. Yields: 50% (based on tipo). Anal. Calcd for C80H94Cd3N20O24P2: C, 45.34; H, 4.47; N, 13.22. Found: C, 45.45; H, 4.55; N, 13.30. Synthesis of 2 A mixture of Zn(NO3)2·6H2O (0.0298g, 0.2mmol), tipo (0.0476g, 0.1mmol), H2bpdc (0.0242g, 0.1mmol), DMF (8ml), methanol (1ml) and HNO3 (1ml, 0.2M) was placed in a Teflon reactor (20ml) and heated at 80°C for 2 days and then cooled to room temperature. The colorless crystals were washed with ethanol and air-dried. Yields: 70% (based on tipo). Anal. Calcd for C240H248N40O48P4Zn8: C, 56.43; H, 4.89; N, 10.97. Found: C, 56.54; H, 4.81; N, 10.85. Synthesis of Ln3+@2 (Ln=Eu and Tb) 30 mg of 2 was immersed in a DMF solution of nitrate salts of Eu3+ and Tb3+ (5 mL, 1 mmol) at 60oC for two days. The product was collected by centrifugation, washed with ethanol several times to remove the residual Ln3+ and dried at room temperature. Cr2O72- maximum adsorption study The adsorption isotherms and relevant parameters can be obtained by fitting against the Langmuir isotherm model:


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Qe=Qm*Ce/(1+KSCe) where Ce is the equilibrium solution concentration (mg/L), Qe (mg/g) is the adsorption amount at different equilibrium solute concentration, Qm is the Langmuir maximum adsorption capacity (mg/g) and Ks is the Langmuir adsorption constant. X-ray Crystallography Single-crystal XRD data for 1 and 2 were recorded on a Bruker Smart Apex II diffractometer with graphitemonochromatized Mo Kα radiation (λ = 0.71073 Å) at 120(2) K. Absorption corrections were applied using the multiscan technique. The structures of these two compounds were solved with SHELXT and refined with SHELXL.

43

Non-hydrogen atoms were refined with anisotropic temperature

parameters. The hydrogen atoms are fixed to appropriate distances and refined from the electron density map. For disordered solvent molecules in the structure, the PLATON/SQUEEZE was applied to remove their diffraction contribution.44 Thus, there were “Alert level A” about “Check Reported Molecular Weight” and “VERY LARGE Solvent Accessible VOID(S) in Structure” in the “checkCIF/PLATON report” files for 1 and 2. Meanwhile, it was also reflected in the check-cif report for 1 and 2 with a ‘B’ level alert about “D-H Without Acceptor” because it was unable to define the hydrogen bonds for the removal of disordered solvent molecules. The final formulas of 1 and 2 were derived from crystallographic data combined with elemental and TGA analysis


6

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data. The detailed crystallographic data and structure refinement parameters are summarized in Table 1. Table 1. Crystal and Structure Refinement Data for Compounds 1 and 2. param

1

2

formula

C80H94Cd3N20O24P2

C240H248N40O48P4Zn8

fw

2118.89

5107.62

space group

P-1

P-1

a

11.2676(5)

16.8876(12)

b

14.9687(6)

19.3356(14)

c

16.0069(7)

19.6846(14)

α (deg)

108.0980(10)

75.6530(10)

β(deg)

95.8340(10)

82.4890(10)

γ (deg)

105.1660(10)

85.718(2)

V

2427.07(18)

6167.8(8)

Z

1

1

Dcalcd (g cm-3)

1.450

1.375

GOF on F2

1.059

1.128

R1/wR2[I≥2sigma(I)]

0.0273/0.0781

0.0631/0.1532

R1/wR2 (all data)

0.0337/0.0798

0.1046/0.1632

RESULTS AND DISCUSSIONS Structural characterization of 1 Compound 1 crystallizes in a triclinic space group P-1. Asymmetric unit consists of two Cd2+ cations, one tipo ligand, one formate anion, and half of bdc2-. The formate anion was generated through the hydrolysis of DMF molecules under solvothermal


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Page 8 of 27

conditions. As shown in Fig. 1a, the Cd1 is coordinated by four N atoms from four tipo ligands and two O atoms from two formate anions. The Cd2 is ligated by one N atom from one tipo and five O atoms from one bdc2- anion, one tipo ligand and one formate anion. Cd2+ to O/N bond distances and valence angles are within the normal range (Table S1). The formate anion coordinates two Cd2+ cations in syn,syn,anti-mode. The bdc2- ligand connects two Cd2+ cations by two chelate carboxylate. The tipo ligand coordinates four Cd2+ in quadrydentate mode forming bonds N2-Cd1A, N6-Cd1B, N4Cd1A, and O1-Cd2B. Within the structure, the bdc2- linker penetrates the ring {(Cd1)2(tipo-N,N′)2} (Fig. 1b). The short HCOO- anions stitch the neighboring Cd-tipo layers, and the long bdc2anions bind two alternating layers separated by one intermediate layer. The three arms of tipo ligands are aligned along arms of other three tipo, they participate in π-π stacking and formation of rings {(Cd2)2(tipo-O,N)2} and {(Cd2)2(HCOO)2(tipo-O,N)2} (Fig. S1). From the topological point of view, the underlying net of the compound 1 in standard representation of ToposPro package contains 4-coordinated nodes of tipo and Cd2, and 6-coordinated nodes of Cd1 (Fig. 1c).45-47 The resulting 4,6-coordinated 3D net belongs to a new topological type with point symbol (4.5.62.72)2(42.54.64.73.92)(42.64)2. We gave name cnk1 to the net, which was added to TTD database of program package ToposPro

(https://topcryst.com/).

The

cnk1

contains

nine

symmetrically

and

topologically different strong rings of minimal sizes 4 (4a, 4b), 5 (5a), 6 (6a, 6b, 6c, 6d),


8

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and 10 (10a, 10b). We found that cnk1 net is self-catenated, since three rings 4b, 10a and 10b catenate each other to form bouquets of 4, 6 and 6 rings respectively (Table S2). Thus, the pattern of rings catenations can be described by 4,6-coordinated 3D Hopf ring net with point symbol (44·610·8)2(64·82). The catenation is a result of only penetration of the 4-ring by an edge, which are corresponded to {(Cd1)2(tipo-N,N′)2} ring and bdc2linker, respectively (Fig. 1b). Therefore a subnet (topological type 3,4,6T53) constructed only by formate and tipo linkers with Cd2+ does not contain catenations of rings. The tipo ligand with Cd2+ construct 3,4-coordinated 2D subnet of well-known topology bex (highlighted by green, yellow and purple in Fig. 1c).48 Calculation in Platon shows 44.7 % of solvent accessible porosity. Moreover, the largest 1D channel spreading along the a axis has the minimal radius Rf(1D) = 3.6 Å (Fig. 1d). From our experience, we know only three isostructural families of other self-catenated frameworks with wider channels (in standard representation of ToposPro) (Table S3).


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Fig. 1. (a) The coordination environment of Cd2+ atoms in 1. The hydrogen atoms are omitted for clarity. (b) View of the penetration of the 4-ring {(Cd1)2(tipo-N,N′)2} by bdc2linker. (c) The underlying net in compound 1. The edges presenting linkers HCOO- and bdc2- arms are highlighted by blue and dark red, respectively. The edges corresponded to tipo arms and highlighting different Cd-tipo sub-layers are in green, yellow and purple. (d) The 1D channels along the a axis. Structural characterization of 2 Compound 2 crystallizes in a triclinic space group P-1. In the structure, there are four crystallographically unique Zn2+ cations, four bpdc2- anions, two tipo ligands and two OH- groups. As shown in Fig. 2a, all the Zn2+ cations adopt distorted tetrahedral geometry. Zn1 and Zn4 are both coordinated by one N atom from one tipo ligand and


10

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three O atoms from one OH- group and two bpdc2- anions. Zn2 and Zn3 are both coordinated by two N atoms from two tipo ligands and two O atoms from one OHgroup and one bpdc2- anion. Zn2+ to O/N bond distances and valence angles are within the normal range (Table S4). All bpdc2- anions connect two Zn2+ atoms by two monodentate carboxylates. Both tipo ligands coordinate three Zn2+ cations by three N atoms leaving oxygen donor atom of P=O group unreacted. One Zn1 and Zn2 are combined by one µ2-bridging OH- group to build a {Zn2O} dimer. The same is for Zn3 and Zn4. Within the structure, the {Zn2O} dimers are connected by bpdc2- anions to give rise to 3-coordinated 2D hcb subnet (Fig. 2b). The tipo liands join the {Zn2O} dimers to generate 1D 3-coordinated subnets of topology (4,4)(0,2) (Fig. 2c). These two nets are interconnected into the new 3,6-coordinated net with the point symbol of (42·610·83)(42·6), in which the {Zn2O} dimers are considered as the 6-coordinated nodes and the tipo ligands are simplified as the 3-coordinated nodes (Fig. 2d and 2e). However, underlying net

in

standard

representation

is

3,4-coordinated

with

point

symbol

(4.6.83.10)(4.6.8)(6.84.10) (Fig. S2), and we added it in the ToposPro topological collection under new name cnk2 (https://topcryst.com/).47 Further, the 4-rings of subnet (4,4)(0,2) are penetrated by edges of bpdc2-, and the 6rings of subnet hcb are penetrated by arms of tipo (Fig. 2f). Together these penetrations produce very complicated 3D self-catenation with the participation of 78 different rings, and the number of catenations of one ring with others from 16 to 140 (Table S5). There is


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a 2D system of channels in the (100) crystallographic plane with minimal radius Rf(2D) = 1.67 Å, maximal radius Ri = 3.2 Å and 32.9 % of unit cell volume. The widest channel with Rf(1D) = 1.7 Å spreads along the b axis (Fig. 2d). The total void space accounts for approximately 37.5% of the whole crystal volume as obtained by PLATON analysis. Interestingly, the uncoordinated P=O groups of tipo point into the channels, which can act as the potential coordinative moiety for lanthanide ions.

Fig. 2. (a) The coordination environment of Zn2+ cations in 2. The hydrogen atoms are omitted for clarity. (b) The perspective view of 3-coordinated 2D hcb subnets generated by the {Zn2O} dimers and bpdc2- anions. (c) The perspective view of 1D 3-coordinated subnets constructed by the {Zn2O} dimers and tipo liands. (d) The perspective view of framework of 2 (the uncoordinated P=O marked by green) and (e) corresponding 3,6coordinated underlying net. (f) The schematic view of the self-catenation in 2. Adsorption capability of 1 towards Cr2O72-


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Inspired from the high pore volume and cationic framework of compound 1 determined from structural studies, we decided to explore its potential for application in the Cr2O72- adsorption. For this 10 mg of 1 was immersed in 15 mL of K2Cr2O7 aqueous solutions (50 mg L-1), respectively. The clear solution after centrifuging was measured by UV/vis spectra at 350 nm to monitor the Cr2O72- concentration at different time intervals. As shown in Fig. 3a, Cr2O72- concentration decreased quickly to 43% in one minute. In about 120 minutes, over 78% Cr2O72- can be removed from the aqueous solution. The result indicates that the Cr2O72- in solution promptly entered into the channels in 1 by exchanging NO3-, which can be confirmed by IR spectra for the disappearance of the broad band arising from NO3- at 1380 cm-1 (Fig. S7). To further evaluate the adsorption maximum of 1 toward Cr2O72-, different concentrations of Cr2O72- solution in the range of 50-700 mg L-1 were used to determine the uptake. As shown in Fig. 3b, the overall adsorption capacity of 1 for Cr2O72- reaches up to 124.4 mg g-1, which ranks among the highest Cr2O72- adsorption in MOF materials ever reported.49-52 In addition, the Langmuir isotherm has been applied to evaluate their maximum adsorption capacity with the correlation coefficient of 0.9838 (Fig. 3b). Accordingly, the calculated maximum adsorption capacity of 1 for Cr2O72- is 128.3 mg g1,

which is approximate to the experimental value. Meanwhile, the release tests were

also carried out to evaluate the regeneration ability of the ion exchanger. The release efficiency of Cr2O72- was high: up to 92% after immersion of Cr2O72-@1 in a saturated


13


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KNO3 solution during 120 minutes (Fig. S6). Further, the PXRD of compound 1 immersed in water after two days shows that the framework does not collapse and show good water stability. It should be noted that after the release of Cr2O72-, although some peaks in the PXRD were weakened, the framework still keeps its integrity (Fig. S3).

Fig. 3. (a) The plots of UV/vis spectra for 15 mL of K2Cr2O7 aqueous solutions (50 mg L1)

after addition 10 mg of compound 1 and further centrifugation to monitor the Cr2O72-

concentration at different time intervals. (b) The Langmuir isotherm to evaluate the maximum adsorption capacity with the correlation coefficient of 0.9838. Photoluminescence properties of Ln3+@2 (Ln3+ = Eu3+ and Tb3+) As was elucidated from the structural analysis, the presence of uncoordinated P=O group protruding into the channels of compound 2 gave us an opportunity to study cations adsorption and corresponded structure modification abilities of the framework. Thus we have discovered the good affinity of P=O group to lanthanide cations. The Eu3+


14

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and Tb3+ ions have been introduced into the 1D channels of 1 by soaking the samples in DMF solutions of their nitrate salts. The loading of Ln3+ does not influence the crystal structure integrity of 2, as demonstrated by PXRD profiles (Fig. S4). Comparing to the FT-IR spectrum of 2 and Eu3+@2, the characteristic absorbance of NO3- (1350 cm-1) in Eu3+@2 indicates the introduction of Eu(NO3)3 into the channels (Fig. S8). Upon excitation at 333 nm, the Eu3+@2 displays narrow luminescence originating from the Eu(III) lowest emitting state 5D0 to 7F0 (578 nm), 7F1 (591 nm), 7F2 (615 nm), 7F3 (650 nm) and 7F4 (695 nm) levels (Fig. 4a).53 The most intense peak at 615 nm corresponds to the 5D →7F 0 2

transition, yielding an intense red color emission. Excited at 254 nm under UV-

light, Eu3+@2 showed bright red light, which can be easily observed by the naked eyes, as shown in the inset of Fig. 4a. Moreover, Eu3+@2 exhibits a long emission lifetime (1.07 ms),54 further demonstrating that MOF 2 can serve as an efficient scaffold for hosting and sensitizing Eu3+ (Fig. 5a). For Tb3+@2, when excited at 337 nm, the emission lines located at about 488, 542, 582, and 616 nm, which can be assigned to 5D4-7FJ (J = 6, 5, 4, 3) transitions of Tb3+ (Fig. 4b).55 For Eu3+@2, the emission of 2 is hardly detected, suggesting the efficient energy transfer between the ligand and Eu3+. While, for Tb3+@2, the ligand-centered emission band located at about 428 nm is obvious, which means the energy transfer between the ligand and Tb3+ is not as strong as between the ligand and Eu3+ (Fig. 4b).


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Page 16 of 27

Fig. 4. (a) Room temperature excitation (black) and emission (red) spectra of the Eu3+@2. (b) Room

temperature excitation (black) and emission (green) spectra of the Tb3+@2.

Fig. 5. (a) The experimental (black) and calculated (red) luminescence decay plots for Eu3+@2 for a peak at 616 nm after excitation at 333 nm. (b) The experimental (black) and calculated (green) luminescence decay plots for Tb3+@2 for a peak at 582 nm after excitation at 337 nm. CONCLUSIONS


16

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In this work, using tripodal phosphine oxide-centered ligand in a mix with dicarboxylate ligands and d-metals cations, we successfully assembled two novel selfcatenated metal-organic frameworks. Compound 1 exhibits a cationic 4,6-connected self-penetrating framework with large 1D channels, which shows a high adsorption for dichromate up to 124.4 mg g-1. Compound 2 features a 3,4-connected self-catenated framework with potential O-donor located on the surface of the channels. Post-synthetic modification of 2 by lanthanide ions (Eu3+ and Tb3+) afforded fluorescent materials. The results show that tris[4-(1H-imidazol-1-yl)]phosphine oxide can act as a 3- or 4coordinated N,O-donor ligand. Such interesting coordination behaviors inspired us to focus on the structures and properties of more MOFs constructed from tipo with versatile polycarboxylate ligands and metal ions.

ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Selected bond lengths and angles, crystallographic data and structure refinement parameters, TGA curves, PXRD, IR spectra, UV/vis spectra and additional figures. Accession Codes CCDC 1914811 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by


17


emailing

[email protected],

or

by

Page 18 of 27

contacting

The

Cambridge

Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author *(X. G.) E-mail: [email protected]. *(H. G.) Fax:+86-431-86168210. E-mail: [email protected]. *(E. A.) E-mail: [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors gratefully acknowledge the financial support for this work from the National Natural Science Foundation of China (No. 21601019), Jilin Natural Science Foundation of China (No. 20160414031GH), Natural Science Foundation of Changchun Normal University (cscxy2017004, cscxy2017028). Eugeny V. Alexandrov thanks Russian Science Foundation (grant No. 18-73-10116) and Russian Ministry of Education and Science (grant No. 1.6101.2017/9.10) for financial support of development of methods for topology and voids analysis, respectively.


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SYNOPSIS

Two novel self-catenated metal-organic frameworks (cnk1 and cnk2) with large accessible channels obtained by mixed-ligand strategy from a tripodal N,O-donor ligand. cnk1 shows a high adsorption for dichromate up to 124.4 mg g-1. Post-synthetic modification of cnk2 by lanthanide ions (Eu3+ and Tb3+) afforded fluorescent materials.


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Two Novel Self-Catenated MetalâOrganic Frameworks with Large

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