Linker desymmetrization: Access to a series of rare-earth tetracarboxylate frameworks with eight-connected hexanuclear nodes

Xiu-Liang Lv, Liang Feng, Lin-Hua Xie, Tao He, Wei Wu, Kun-Yu Wang, Guangrui Si, Bin Wang,

Article

Linker Desymmetrization: Access to a Series of Rare-Earth

Tetracarboxylate Frameworks with Eight-Connected Hexanuclear

Nodes

Jian-Rong Li,* and Hong-Cai Zhou *

Cite This: J. Am. Chem. Soc. 2021, 143, 2784 −2791

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sı Supporting Information

ABSTRACT: The exploration of metal−organic frameworks

MOFs) through the rational design of building units with speciﬁc

(

sizes, geometries, and symmetries is essential for enriching the

structural diversity of porous solids for applications including

storage, separation, and conversion. However, it is still a challenge

to directly synthesize rare-earth (RE) MOFs with less connected

clusters as a thermodynamically favored product. Herein, we report

a systematic investigation on the inﬂuence of size, rigidity, and

symmetry of linkers over the formation of RE-tetracarboxylate

MOFs and uncover the critical role of linker desymmetrization in

constructing RE-MOFs with eight-connected hexanuclear clusters.

Our results on nine new RE-MOFs, PCN-50X (X = 1−9), indicate

that utilization of trapezoidal or tetrahedral linkers provides

accesses to traditionally unattainable RE-tetracarboxylate MOFs with 8-c hexanuclear nodes, while the introduction of square or

rectangular linkers during the assembly of RE-MOFs based on polynuclear clusters typically leads to the MOFs constructed from 12-

c nodes with underlying shp topology. By rational linker design, MOFs with two unprecedented (4, 8)-c nets, lxl and jun, can also be

obtained. This work highlights linker desymmetrization as a powerful strategy to enhance MOFs’ structural complexity and access

MOF materials with nondefault topologies that can be potentially used for separation and catalysis.

INTRODUCTION

unusual topologies and properties for applications in sensing,

catalysis, and separation.

Among metals utilized for MOF construction, rare-earth (RE)

elements have recently attracted increasing attention because

they can form more adaptable RE polynuclear clusters including

■

12−14

Ligand design plays an essential role in the prediction and

construction of metal−organic frameworks (MOFs) with ideal

pore environments for applications including separation,

storage, and conversion. Through rational design of building

blocks with speciﬁc sizes, geometries, and symmetries, frame-

work materials with predetermined topologies and optimized

pore spaces can be accessed. For instance, Yaghi and co-

workers adjusted symmetry of a ditopic linker, 4,4′-biphenyldi-

carboxylate (bpdc), by altering the locations of linker

substituents to control the formation of a two-dimensional

−6

RE , RE , RE , and RE clusters that can function as building

blocks for the assembly of diverse topologies with high

connectivity. Notably, there are some similarities between

Zr-MOFs and RE-MOFs; for example, fcu topology can be

found in both Zr-MOFs and RE-MOFs when linking [Zr (μ -

O) (μ -OH) ] or [RE (μ -OH) ] clusters with ditopic linkers,

6−19

MOF-118 and a three-dimensional MOF-601. In MOF-118,

respectively.

Yet, one major diﬀerence between Zr-MOFs

the two carboxylate-group planes are close to coplanar, while

they are perpendicular to each other in MOF-601 due to the

bulk of the linker substitutes. A similar concept has also been

introduced into Zr-MOFs later, for example, the formation of

UiO-67 with coordinatively saturated clusters and PCN-700

with open pockets that allow for the installation of linkers with

and RE-MOFs is that less connected clusters are rarely observed

in RE-MOFs but are common in Zr-MOFs. For example, when

the tritopic linker BTB is involved, Zr-BTB interpenetrated

3−

Received: November 3, 2020

Published: January 25, 2021

varying lengths and combinations. Recently, Guillerm,

Maspoch, and co-workers provided a summary on this topic,

where they described a “geometry mismatch” concept to

assemble MOFs with nondefault topologies. These progresses

provide fresh insights into the design of complex MOFs with

2021 American Chemical Society

J. Am. Chem. Soc. 2021, 143, 2784−2791

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Article

20,21

networks or nanosheets with 6-c Zr cluster are obtained

while gea-MOF-1(RE) crystals with fully coordinated 18-c RE₉

clusters are assembled, without the observation of less

3−

connected RE clusters. When the tritopic linker TATB is

involved, PCN-777 crystals with 6-c Zr cluster are obtained,

while sph-MOF-4(RE) crystals can only form with the

assistance of a secondary tritopic linker, which ensures the

formation of fully coordinated 12-c RE clusters. The reason

behind this phenomenon is because the RE cation allows for

multiple directionality of coordinated ligands, and each cation

can coordinate with 6−12 terminal ligands, while the coordinate

25−27

number of Zr cation is eight.

Therefore, the less connected

RE clusters will inevitably destabilize the framework and usually

lead to the formation of other thermodynamically favored

products. A typical example is PCN-900(RE) constructed from

Figure 1. Reported topologies (ftw, shp, ﬂu, and hjz) and newly

discovered topologies (scu, lxl, and jun) in RE-tetracarboxylate MOFs

built on RE or RE clusters.

4−

TCPP linkers. In Zr-MOFs, there are multiple phases

including PCN-222 with 8-c Zr clusters and PCN-224 with 6-c

Zr clusters formed during the assembly of Zr clusters and TCPP

linkers. However, these structures are inaccessible in RE-MOFs

without the addition of an auxiliary linker to fulﬁll the fully

connected RE clusters.

Most reported RE-MOFs constructed from tetratopic linkers

contain fully connected RE clusters. Eddaoudi and co-workers

employed a series of square and rectangular linkers during the

synthesis of RE-MOFs and obtained MOFs with 4,12-c ftw and

9−31

,12-c shp topologies.

Li and co-workers further

introduced two rectangular linkers to assemble RE-MOFs for

2,33

separation.

MOFs with ftw topology were harvested;

however, the MOF with predicted 4,8-c scu topology was failed

to fabricate, showing the challenges lying in the direct synthesis

of RE-MOFs with less connected RE clusters. Very recently,

Trikalitis and co-workers reported two RE-MOFs based on

tetrahedral linkers: 4,12-c RE-hpt-MOF-1 and 4,8-c RE-ken-

MOF-1. Further development of RE-MOFs with less

connected RE clusters requires enhanced understanding on

the inﬂuence of linker symmetry over the formation of

frameworks. Herein, we uncover the importance of linker

desymmetrization in accessing RE-tetracarboxylate MOFs with

-connected RE clusters. Structural studies of nine new MOFs,

Figure 2. Tetracarboxylate linkers (L1−L9) with diﬀerent sizes,

PCN-50X (X = 1−9), constructed from tetracarboxylate linkers

with varying sizes, rigidities, and symmetries reveal that

utilization of trapezoidal or tetrahedral linkers provides accesses

to traditionally unattainable RE-tetracarboxylate MOFs with 8-c

hexanuclear nodes. The introduction of square or rectangular

linkers during the assembly of RE-MOFs based on polynuclear

clusters typically leads to the MOFs constructed from 12-c

nodes with underlying shp topology. By rational linker design,

MOFs with unprecedented (4, 8)-c nets including lxl and jun

can also be obtained (Figure 1). This work highlights the role of

linker desymmetrization in accessing MOF materials with

nondefault topologies, which can function as a powerful strategy

to enhance structural complexity of MOFs. The potentially

unsaturated metal sites within these 8-connected hexanuclear

nodes can be used for guest binding during separation and

catalysis processes.

rigidities, and symmetries used in this work.

PCN-501 crystals with a shp topology. It contains a 12-

connected [RE (μ -OH) (μ -O) (O C−) ] cluster as a

hexagonal prism node and a tetratopic linker as a joint

rectangular node. Additionally, under the same condition, the

reaction between Eu(NO ) ·6H O and H L2 also yields PCN-

02 crystals with the same topology because of the same

4−

conformations and geometries of L1 and L2 . It should be

noticed that the Tb and Y-based MOFs with shp topology,

named CU-10, have been recently reported by Howarth and co-

workers. This observation is consistent with previous reports

that the introduction of a rectangular linker into 2-FBA

modulated RE-MOFs will generate a shp topology (Figure 3).

−1

Saturated N uptakes of 652 and 517 cm g (STP) are

achieved, and the BET surface areas of PCN-501 and -502 are

RESULTS AND DISCUSSION

2 −1

■

estimated to be 2277 and 1978 m g , respectively (Figures S32

and S33 ). The pore volumes are calculated to be 1.01 and 0.80

RE-Tetracarboxylate MOFs Based on Rectangular

Linkers. Herein we selected nine tetratopic linkers with various

sizes, rigidities, and symmetries to explore the structures and

topologies of RE-MOFs (Figure 2). With the modulation of 2-

ﬂuorobenzoic acid (2-FBA), solvothermal reactions between

rectangular H L1 and Eu(NO ) ·6H O for 48 h yielded large

−1

cm g , respectively.

RE-Tetracarboxylate MOFs Based on Tetrahedral

Linkers. To study the eﬀects of linker geometry over structural

formation, methyl groups are added onto the two central phenyl

rings in the examples of H L3 and H L4. This modiﬁcation

3 3

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Figure 3. Structures and topologies of PCN-50X (X = 1−4). (a)

Linking of 4-c rectangular linkers (L1 and L2) with 12-connected RE

clusters leads to the formation of PCN-501 and PCN-502 (shp

topology). (b) Employment of 4-c tetrahedral linkers (L3 and L4)

prompts the formation of PCN-503 and PCN-504 (ﬂu topology)

constructed from 8-connected RE clusters. RE, C, O, and N atoms are

represented by turquoise, gray, red, and blue, respectively, and H atoms

are omitted for clarity.

Figure 5. Proposed formation mechanism of diﬀerent topologies using

L5 and L6. (a) Installation of rectangular linkers into frameworks based

on scu net leads to the formation of PCN-505 with a shp net. (b) A scu

net can also form by using a trapezoidal building unit; however, it does

not allow for the installation of trapezoidal building blocks into the

open pockets due to size mismatch.

were considered to be very rigid linkers due to the presence of

the 2,2′,6,6′-tetramethylbiphenyl core. Because of the steric

hindrances of neighboring methyl groups, the orientation of the

two central phenyl rings is strongly constrained. The clusters

were found to be 8-connected RE clusters, similar to 8-c Zr

clusters in widely studied Zr-MOFs. Saturated N uptakes of 632

−1

and 485 cm g (STP) are achieved, and the BET surface areas

of PCN-503 and -504 are estimated to be 2715 and 1616 m g ,

respectively (Figures S34 and S35). The pore volumes are

−1

calculated to be 0.98 and 0.76 cm g , respectively.

RE-Tetracarboxylate MOFs Based on Trapezoidal

Linkers. RE-MOFs based on linkers with a reduced symmetry,

such as a trapezoidal shape, have not been fully investigated yet.

When replacing the pyrene core with a carbazole core in the

tetracarboxylates, the linker symmetry can be decreased to C_s

accordingly. Solvothermal reactions between Eu(NO ) ·6H O

and trapezoidal linker H L5 in the presence of 2-FBA for 48 h

yielded large colorless crystals, PCN-505 with a (4, 12)-c shp

topology (Figure 4c). It is traditionally observed that the

selection of contracted or expanded linkers will not alter the

underlying topology of a MOF structure under the same

Figure 4. Structures and topologies of PCN-50X (X = 5, 6). (a) Organic

linkers rectangular L5 and trapezoidal L6 display diﬀerent geometries in

extended frameworks. (b) Structural illustration of PCN-505 and PCN-

reaction conditions. However, in this case, the employment of

506. (c) Underlying scu and shp topologies of PCN-505 and PCN-506,

4−

respectively. RE, C, O, and N atoms are represented by turquoise, gray,

red, and blue, respectively, and H atoms are omitted for clarity.

its contracted version L6 prompts the formation of PCN-506

with a diﬀerent (4, 8)-c scu topology in RE-MOFs. To the best

of our knowledge, this topology has not been discovered in RE-

MOFs, although it is common in Zr-MOFs. Single-crystal X-ray

diﬀraction (SCXRD) provides direct information about the

alters the original rectangular geometry into a tetrahedral shape.

The assembly of tetrahedral H L3/H L4 and hexanuclear RE

4−

clusters prompts the formation of PCN-503/504 with a (4,8)-c

geometry of L5 /L6 in the MOF structures, which allows for

−

4−

ﬂu topology (Figure 3). In these two cases, the linker L3 /L4

the investigation of formation mechanism of diﬀerent top-

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Figure 6. Topological comparison between (6, 12)-c alb net and (4, 8)-c lxl net. (a) Use of a 6-c triangular prism linker (disordered L7) resulted in the

formation of disordered PCN-507 with underlying alb topology. (b) Utilization of a 4-c tetrahedral linker (L7) resulted in the discovery of PCN-507

with a new lxl topology. RE, C, O, and N atoms are represented by turquoise, gray, red, and blue, respectively, and H atoms are omitted for clarity.

Figure 7. Schemes showing structures and topologies of PCN-507 with and without disorder. (a) Insertion of 6-c triangular prism linkers between hxl

RE layers results in the assembly of disordered PCN-507 with alb topology. (b) Introduction of 4-c tetrahedral linkers between hxl RE layers can

induce the formation of PCN-507 with lxl topology. RE, C, O, and N atoms are represented by turquoise, gray, red, and blue, respectively, and H atoms

are omitted for clarity.

ologies. It was found that the rigid L6⁴⁻linker with shorter

prohibited due to size mismatch. This explains the importance of

linker desymmetrization in accessing RE-MOFs with relatively

benzoate arms displays a trapezoidal geometry while the ﬂexible

4−

−1

L5 linker with longer naphthoate arms displays a rectangular

geometry in the constrained framework. From a topological

perspective, the formation of a shp net can be viewed as a result

of installation of rectangular building blocks into the open

pockets in a scu net (Figure 5a). Because of the preference for

RE clusters to be fully coordinated, structures with shp topology

formed eventually as a thermodynamic favorable product.

However, trapezoidal building blocks cannot be solely used for

the construction of a shp net because the installation of

trapezoidal building blocks into the open pockets of a scu net is

low connectivity. Saturated N uptakes of 612 and 446 cm g

(STP) are achieved, and the BET surface areas of PCN-505 and

−1

-506 are estimated to be 2401 and 1766 m g , respectively

(Figures S36 and S37 ). The pore volumes are calculated to be

−1

0.96 and 0.69 cm g , respectively.

RE-Tetracarboxylate MOFs Based on Distorted Tetra-

hedral Linkers. Further reduction of linker symmetry by

removing naphthoate units in two side arms was conducted in

−

linker L7 . The free rotation of two other side arms endows the

linker with a distorted tetrahedral shape. Use of the tetrahedral

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Figure 8. Structural and topological analysis of PCN-50X (X = 8, 9). (a) Use of a 4-c distorted tetrahedral linker (L8 and L9) resulted in the formation

of PCN-508 and PCN-509 with underlying jun topology. (b) Structural illustration of PCN-508 and PCN-509. (c) RE hxl layers A and B,

perpendicular to each other, allow for the installation of L8 or L9 to form a 3D pillar-layered structure. (d) Structural comparison between PCN-507

−

4−

and PCN-508: a pair of L7 (α and β) linkers are linked to seven RE clusters in PCN-507 while a pair of L8 (α and β) linkers are only connected to

six RE clusters in PCN-508. RE, C, O, and N atoms are represented by turquoise, gray, red, and blue, respectively, and H atoms are omitted for clarity.

L7⁴linker resulted in the discovery of PCN-507 with a new (4,

)-c lxl topology derived from (6, 12)-c alb topology. Reactions

between Eu(NO ) ·6H O and H L7 in the presence of 2-FBA

−

surface area of PCN-507 is estimated to be 1408 m g (Figure

2 −1

−1

S38 ). The pore volumes are calculated to be 0.57 cm g .

Replacement of the central phenyl core in H L7 with a

carbazole core leads to the generation of H L8, altering the angle

between naphthoate groups on the core from 120° to 90°.

Solvothermal reactions between H L8 and Eu(NO ) ·6H O in

yielded colorless PCN-507 crystals. The SCXRD structure

indicated that PCN-507 crystallizes in the Cmcm space group. It

should be noted that a 6-connected linker (disordered L7) was

observed as a result of crystallographic disorder, which has also

been observed previously.

resulting crystal structure reveals that it reticulates the (6,12)-

3 3

the presence of 2-FBA for 48 h yielded crystals of PCN-508

Figure 8 a,b). PCN-508 crystallized in the C2/c space group

^T ^a ^b ^l ^e ^S ⁶⁾^.^C^r^y^s^t^a^l^l^o^g^r^a^p^hⁱ^c^a^l^l^y^,ⁱ^t^c^oⁿ^t^aⁱⁿ^s^a⁸^-^c^oⁿⁿ^e^c^t^e^d^R^E6

cluster and a distorted tetrahedral linker (Figure 2c,d). The

38,39

(

Topological analysis of the

c alb net, containing a 12-c Eu cluster as a hexagonal prism node

overall structure was analyzed to be a new 4,8-connected jun net

and a 6-c disordered linker as a triangular prism node.

Alternatively, PCN-507 structure can be viewed as a pillar-

layered structure. The hexanuclear RE clusters are placed into

hxl layers while disordered L7 linkers as pillars are inserted

between layers to form a 3-periodic MOF (Figure 7a). To unveil

more structural information, the crystallographic disorder of the

with a point symbol of {4 .6 } {4 .6 .8 } as determined by

TOPOS 4.0. Because of the changes on the linker conformation,

the connectivity mode in PCN-507 and PCN-508 varies. As

4−

shown in Figure 8d, a pair of L7 (α and β) linkers are linked to

−

seven RE clusters in PCN-507 while a pair of L8 (α and β)

linkers are only connected to six RE clusters in PCN-508.

L7 linker was removed by only selecting four intrinsic

Moreover, four clusters linked by one linker are parallel to each

other in PCN-507. Yet, in PCN-508, the orientation of four

clusters linked by one linker is diﬀerent: two of them are

perpendicular to the other two. As a result, there are two types of

RE hxl layers (A and B, Figure 8c) existing in the pillar-layered

structure. Utilization of L9 linker with shorter benzoate arms

4−

carboxylates on each L7 linker. As shown in Figure 6b,

PCN-507 without disorder contains an 8-connected Eu cluster

and a 4-connected distorted tetrahedral linker. The overall

structure was found to be a new 4,8-connected lxl net with a

point symbol of {4 .6 .8 }{4 .6 } {4 .6 .8 } as determined by

TOPOS 4.0 (Figure 7b). In this case, the structure can be

viewed as a result of the installation of tetrahedral L7 pillars

4−

generates isoretcular PCN-509 with jun topology due to the

4−

similarity of geometry and rigidity between L8 and L9 . The

shape of the channels observed in PCN-508 and -509 is

diamondoid; the lengths are estimated to be ca. 12 and 7 Å,

respectively, which match well with the actual size observed in

the pore size distribution (Figures S39 and S40 ) Saturated N

uptakes of 412 and 316 cm g (STP) are achieved, and the

between hxl layers consisting of RE clusters. The largest

diamondoid channels in PCN-507 are along the crystallographic

b direction and relatively small ones in the c directions; the

lengths are estimated to be ca. 8 and 12 Å, respectively. Saturated

−1

N uptakes of 378 cm g (STP) are achieved, and the BET

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Journal of the American Chemical Society

People’s Republic of China; orcid.org/0000-0002-8101-

Article

BET surface areas of PCN-508 and -509 are estimated to be

8493 ; Email: jrli@bjut.edu.cn

Hong-Cai Zhou − Department of Chemistry, Texas A&M

University, College Station, Texas 77843-3255, United States;

orcid.org/0000-0002-9029-3788; Email: zhou@

tamu.edu

−1

549 and 1170 m g , respectively. The pore volumes are

−1

calculated to be 0.65 and 0.49 cm g , respectively.

Stability and Porosity. The permanent porosity of the

PCN-50X(Eu) series was revealed by N sorption isotherms

measured at 77 K, indicating their microporous features (section

in the Supporting Information ). The chemical stability of the

Authors

PCN-50X series was further assessed by immersing them into

varying solvents for 24 h. As indicated by the corresponding

PXRD patterns, the PCN-50X(Eu) series was stable in water

and most organic solvents including acetone, dichloromethane,

acetonitrile, and methanol (Figures S14 −S31). The preparation

of PCN-50X series based on other RE metals such as Y and Yb

was also conducted under similar solvothermal reaction

conditions, with PXRD patterns showing their phase purities

Xiu-Liang Lv − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

People’s Republic of China; Department of Chemistry, Texas

A&M University, College Station, Texas 77843-3255, United

States

Liang Feng − Department of Chemistry, Texas A&M

University, College Station, Texas 77843-3255, United States;

orcid.org/0000-0001-9693-1595

Lin-Hua Xie − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

People’s Republic of China; orcid.org/0000-0003-0017-

Complete contact information is available at:

Figures S14 −S31 ). Overall, our systematic research on the RE-

tetracarboxylate frameworks sheds light on the precise design

and synthesis of organic ligands for the assembly of porous MOF

structures and shall accelerate the discovery of highly connected

networks with unprecedented topologies. Further studies of

these potentially unsaturated RE metal sites within the

hexanuclear nodes in separation and catalysis are currently

ongoing.

3887

Tao He − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

People’s Republic of China; orcid.org/0000-0003-3443-

CONCLUSIONS

■

In conclusion, we report a design strategy, linker desymmetriza-

tion, and its utilization in preparing a series of RE-

tetracarboxylate MOFs with 8-connected hexanuclear nodes.

Depending on the size, rigidity, and symmetry of linkers, various

topologies can be targeted with diverse connectivity modes. The

general conclusion we reach is that utilization of square or

rectangular linkers typically provides accesses to RE-MOFs

based on 12-c polynuclear clusters with underlying ftw or shp

topology, while the introduction of trapezoidal or tetrahedral

linkers during the assembly of RE-MOFs typically leads to the

MOFs constructed from 8-c hexanuclear clusters with under-

lying scu, ﬂu, lxl, or jun topology. This work provides eﬃcient

design strategies for the construction of unprecedented

topologies through linker desymmetrization, which shall further

guide the discovery of MOF materials with nondefault

topologies and unusual structural complexity. The potentially

unsaturated RE sites in aforementioned MOFs are expected to

allow for the installation of a secondary linker and show

enhanced interaction with guest molecules, providing access to

highly eﬃcient storage, separation, sensing, and catalysis.

6243

Wei Wu − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

People’s Republic of China

Kun-Yu Wang − Department of Chemistry, Texas A&M

University, College Station, Texas 77843-3255, United States

Guangrui Si − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

People’s Republic of China

Bin Wang − Fujian Provincial Key Laboratory of Polymer

Materials, College of Chemistry and Materials Science, Fujian

Normal University, Fuzhou 350007, People ’s Republic of

China; orcid.org/0000-0003-2742-5191

https://pubs.acs.org/10.1021/jacs.0c11546

Author Contributions

X.-L.L. and L.F. contributed equally to this work.

ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/jacs.0c11546.

Notes

■

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

The authors acknowledge the ﬁnancial support from the

National Natural Science Foundation of China (No.

■

Text, tables, and ﬁgures giving experimental procedures

for the syntheses of the ligands, PXRD, gas sorption

1771012, 51621003), the Science & Technology Project of

isotherms, H NMR spectra, and other additional

Beijing Municipal Education Committee (KZ201810005004),

and the Robert A. Welch Foundation through a Welch Endowed

Chair to H.C.Z. (A-0030).

information (PDF)

X-ray crystallographic details of PCN-50X (X = 2−9)

(CIF )

REFERENCES

■

AUTHOR INFORMATION

Corresponding Authors

Jian-Rong Li − Beijing Key Laboratory for Green Catalysis and

Separation and Department of Environmental Chemical

Engineering, Beijing University of Technology, Beijing 100124,

■

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NOTE ADDED AFTER ASAP PUBLICATION

■

This paper published ASAP on January 25, 2021 with missing

information. The paper was revised and the updated version was

reposted on January 27, 2021.

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