Three Resorcin[4]arene-Based Two-Dimensional Zn(II) Supramolecular Isomers Synthesized via a Structure-Directing Strategy for Knoevenagel Condensation

Strategy for Knoevenagel Condensation

Article

Three Resorcin[4]arene-Based Two-Dimensional Zn(II)

Supramolecular Isomers Synthesized via a Structure-Directing

Fei-Fei Wang, Ying-Ying Liu,* Wen-Yuan Pei, and Jian-Fang Ma*

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sı Supporting Information

ABSTRACT: Herein, in the presence of three structure-directing

agents (SDAs), a family of imidazole-functionalized resorcin[4]arene-

based coordination polymers (CPs), [Zn(TIC4R)(HCOO)]·HCOO·

.5DMF·1.5H O (1), [Zn(TIC4R)(CN)]·HCOO·DMF·2.5H O (2),

and [Zn(TIC4R)(H O)]·2HCOO·2H O (3), were assembled under

solvothermal conditions [TIC4R = tetra(imidazole) resorcin[4]arene].

exhibits a double-layer structure with rectangle windows, and 2 and 3

display monolayer structures. The layers of CPs 2 and 3 are slides with

diﬀerent oﬀsets along the a-axis. In addition, three CPs were used as

catalysts to catalyze Knoevenagel condensations. Strikingly, all CPs

exhibit remarkable catalytic performance for several substrates. To the

best of our knowledge, this is the ﬁrst time that a small organic acid as

SDA was used in the syntheses of resorcin[4]arene-based supra-

molecular isomers.

INTRODUCTION

separate and reuse the catalysts. Thus, the design and syntheses

of new heterogeneous catalysts have attracted a great deal of

■

Structure-directing agents (SDAs) are becoming an active

research area today, particularly in the ﬁelds of zeolite or

molecular sieve syntheses.

backbone of architectures but act as templates, space-ﬁlling

molecules, or counterions for charge balance in the pores.

4−36

attention.

heterogeneous catalysts because they have insoluble features

In this regard, CPs were often used as

−6

SDAs seldom appear in the ﬁnal

37,38

and uniformly distributed metal ions in their structures.

−9

Because of the considerations described above, we focused

on the construction and properties of resorcin[4]arene-based

(Scheme 1) CPs by introducing organic acids as SDAs. In this

work, three new CPs, [Zn(TIC4R)(HCOO)]·HCOO·

Commonly used SDAs include organic/inorganic acids,

polyoxometalatic acids, organic amines, and solvent mole-

0−12

cules.

preparation of coordination polymers (CPs).

Recently, SDAs began to be employed for the

8,13

By analyzing

previous works, we found that rational utilization of SDAs

0.5DMF·1.5H O (1), [Zn(TIC4R)(CN)]·HCOO·DMF·

could result in diﬀerent structures upon adjustment of the

.5H O (2), and [Zn(TIC4R)(H O)]·2HCOO·2H O (3),

14−16

dimensions of CPs.

were ﬁrst achieved by employing 2-sulfoterephthalic acid,

fumaric acid, and terephthalic acid as SDAs. Meaningfully, all

of the CPs exhibit excellent and recyclable heterogeneous

catalytic performances for Knoevenagel condensations. The

diﬀerent catalytic abilities of three isomeric CPs were

compared on the basis of the sizes of channels in their

structures.

As an important branch of supramolecular chemistry and

crystal engineering, supramolecular isomerism refers to the

phenomenon of diﬀerent networks with the same structural

units. It is an enormous challenge to design a supramolecular

7−22

isomerism system with SDAs.

alized resorcin[4]arenes, plenty of CPs with unique architec-

On the basis of function-

23−29

tures and diverse properties have been reported.

Although

POMs as SDAs have been applied in the syntheses of

resorcin[4]arene-based CPs, small organic acids as SDAs for

the syntheses of resorcin[4]arene-based supramolecular

Received: February 17, 2021

25,30,31

isomers have never before been reported.

As a crucial member of the C−C bond-forming reaction,

Knoevenagel condensation is a typical condensation between

32,33

aldehydes and methylene.

However, this reaction was

usually catalyzed by homogeneous catalysts, and it is hard to

XXXX American Chemical Society

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Article

(

s), 1352 (m), 1283 (w), 1238 (s), 1149 (w), 1106 (s), 1092 (s),

062 (m), 1019 (m), 984 (s), 955 (s), 919 (m), 852 (w), 750 (m),

79 (w), 660 (m), 635 (w), 585 (w), 565 (w).

Scheme 1. Structure of TIC4R

Crystals of 3 (48% yield). Element analysis (%) calculated for

C H ZnN O : C, 57.78; H, 5.03; N, 10.00. Found: C, 58.02; H,

−1

.23; N, 9.67. IR data (KBr, cm ): 3396 (m), 3133 (w), 2972 (m),

593 (s), 1530 (m), 1475 (s), 1459 (s), 1435 (m), 1406 (m), 1359

(s), 1283 (w), 1238 (s), 1150 (w), 1106 (s), 1091 (s), 1063 (m),

018 (m), 984 (s), 956 (s), 920 (m), 894 (w), 856 (w), 816 (w), 799

(w), 755 (s), 679 (w), 661 (m), 634 (w), 586 (w), 567 (m).

RESULTS AND DISCUSSION

■

The SQUEEZE program in PLATON was used to reﬁne the

structures of 1−3, and the formulas of 1−3 were established by

diﬀuse electron density, thermogravimetric analysis, and

elemental analysis.

Structural Description of [Zn(TIC4R)(HCOO)]·HCOO·

EXPERIMENTAL SECTION

■

.5DMF·1.5H O (1). 1 crystallized in a tetragonal system, in

Synthesis of [Zn(TIC4R)(HCOO)]·HCOO·0.5DMF·1.5H O (1).

space group I4/m (Table 1). The independent unit of 1

A mixture of TIC4R (9 mg, 0.01 mmol), Zn(NO ) ·6H O (12 mg,

contains a quarter of a TIC4R ligand, a quarter of a Zn(II)

.04 mmol), 2-sulfoterephthalic acid monosodium salt (11 mg, 0.04

−

mmol), and 3.5 M HNO (two drops) was added to a DMF/H O

cation, and a quarter of a HCOO anion. A quarter of a free

−

solution [8 mL, 3/5 (v/v)] in a 15 mL Teﬂon reactor. Then, the

mixture was heated at 110 °C for 3 days. The crystals were formed in

a 45% yield based on TIC4R. Elemental analysis (%) calculated for

C H ZnN O : C, 59.54; H, 5.09; N, 10.73. Found: C, 59.22; H,

HCOO anion ﬂoats in the framework to balance the cationic

charge. The formula unit also contains half of a free DMF

molecule and one and a half free H O molecules. The Zn(II)

8.5 13

cation is ﬁve-coordinated with four N atoms from four

−

(

.01; N, 10.85. IR data (KBr, cm ): 3412 (w), 3132 (w), 2972 (m),

593 (s), 1531 (m), 1475 (s), 1460 (s), 1434 (m), 1405 (m), 1379

−

diﬀerent TIC4R ligands and a HCOO anion (Figure 1a).

Each TIC4R ligand connects with Zn(II) ions in a tetradentate

m),1357 (m), 1304 (m), 1283 (w), 1238 (s), 1149 (m), 1106 (s),

092 (s), 1062 (m), 1019 (s), 983 (s), 954 (s), 919 (s), 852 (w), 798

w), 752 (m), 679 (w), 660 (m), 621 (w), 585 (w), 565 (w), 499

w).

−

mode. It is worth noting that C14 of the HCOO anion lies at

an inversion center, and the Zn(II) ions are linked by

−

symmetry-related HCOO anions and TIC4R ligands to

Syntheses of [Zn(TIC4R)(CN)]·HCOO·DMF·2.5H O (2) and

generate a double layer (Figure 1b). The cavitands of TIC4R

are arranged in a face-to-face manner to aﬀord a channel with

dimensions of ∼10.3 Å × 2.4 Å when the van der Waals radii

of the atoms are taken into account (Figure 1c and Figure

S3a ).

[

Zn(TIC4R)(H O)]·2HCOO·2H O (3). CPs 2 and 3 were prepared by

2 2

an experimental procedure identical to that of 1 except that 2-

sulfoterephthalic acid monosodium salt was replaced with fumaric

acid (4 mg, 0.04 mmol) and terephthalic acid (7 mg, 0.04 mmol),

respectively.

Structural Descriptions of [Zn(TIC4R)(CN)]·HCOO·

Crystals of 2 (44% yield). Element analysis (%) calculated for

C H ZnN O : C, 58.64; H, 5.27; N, 12.00. Found: C, 58.19; H,

DMF·2.5H O (2) and [Zn(TIC4R)(H O)]·2HCOO·2H O (3).

10 13.5

−

.93; N, 12.61. IR data (KBr, cm ): 3394 (m), 3132 (w), 2971 (w),

668 (s), 1604 (s), 1522 (m), 1475 (s), 1434 (w), 1405 (m), 1384

When diﬀerent SDAs were used during the reaction, two other

supramolecular isomers were obtained. Crystallographic

Table 1. Crystallographic Data for CPs 1−3

formula

M_r

crystal system

space group

a (Å)

b (Å)

c (Å)

α (deg)

β (deg)

γ (deg)

V (Å³)

C H ZnN₈_.₅O₁₃

C H ZnN O

1167.52

triclinic

C H ZnN O

57 61

10 13.5

54 56

1109.45

tetragonal

I4/m

13.8032(3)

32.399(3)

1122.43

tetragonal

P4/n

13.79650(10)

15.8622(4)

13.7747(6)

13.8337(8)

17.0114(10)

111.443(6)

99.500(5)

90.175(4)

2968.7(3)

6172.9(6)

3019.27(9)

T (K)

298

1.194

2318

298

1.306

1222

298

1.235

1172

D_c_a_l_c(g/cm⁻³)

F(000)

R_i_n_t

0.0771

1.024

0.0572

0.1850

0.0428

0.970

0.0727

0. 2268

0.0229

1.052

0.0473

0.1436

goodness of ﬁt on F

R₁[I > 2σ(I)]

wR₂(all data)

R = ∑||F | − |F ||/∑|F |. wR = {∑[w(F − F ) ]/∑w(F ) }1/2_.

2 2

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Article

Figure 1. (a) Coordination sphere of Zn(II) in 1 . (b) Layered structure of 1. (c) Two-dimensional packing structure of 1.

Scheme 3. Knoevenagel Condensations with Meldrum’s

Acid and Barbituric Acid

Table 3. Knoevenagel Condensations of Meldrum’s Acid

and Barbituric Acid with Benzaldehyde Catalyzed by 1−3

entry catalyst substrate time (min) temp (°C) conversion (%)

Figure 2. (a) Coordination sphere of Zn(II) in 2. (b) Two-

dimensional packing structure of 2. (c) Coordination sphere of Zn(II)

in 3. (d) Two-dimensional packing structure of 3.

Scheme 2. Schematic Drawing for the Knoevenagel

Condensations

−

is diﬀerent (Figure 2a,c). In CP 2, the coordinated HCOO

anion is replaced by the CN anion and the CN⁻is

−

monodentate, so the Zn(II) ions are linked by TIC4R ligands

−

to give a monolayer. The CN is produced by the

decomposition of DMF under hydrothermal conditions. In

−

Table 2. Knoevenagel Condensation of Malononitrile with

Benzaldehyde under Various Conditions

CP 3, the coordinated HCOO is replaced by a H O molecule,

and the structure is also a monolayer. The second diﬀerence

lies in the slide of the layers (Figure 2b,d). For 2, the layer

moves along the a-axis for ∼4.16 Å, forming a channel with

dimensions of ∼6.3 Å × 1.9 Å when the van der Waals radii of

the atoms are taken into account (Figure S3b). For 3, a

signiﬁcant slide of ∼6.90 Å along the a-axis results in a channel

with dimensions of 4.2 Å × 1.7 Å when the van der Waals radii

of the atoms are taken into account (Figure S3c). The levels of

slide lead to diﬀerent channels of three CPs, and the order of

the channel size is as follows: 1 > 2 > 3.

Knoevenagel Condensation. Considering the Lewis acid

Zn(II) sites in 1−3, their catalytic performances for

Knoevenagel condensation were evaluated under solvent-free

conditions (Scheme 2). The conversions were calculated by

gas chromatography (GC) (Figure S5). Before the catalytic

reaction, the crystals of 1−3 were soaked in acetone for 12 h

and then heated at 80 °C under vacuum for 12 h. To

investigate the optimum reaction parameters, the model

entry

catalyst

none

Zn(NO ) ·6H O

time (min) temp (°C) conversion (%)

trace

>99

TIC4R

With 0.50 mmol % 1.

analysis shows that the Zn(II) ions in 2 and 3 also exhibit

pyramidal geometries. There are some diﬀerences among the

three CPs. First, the axially coordinated molecule of Zn(II) ion

Inorg. Chem. XXXX, XXX, XXX−XXX

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Article

Table 4. Diﬀerent Knoevenagel Condensations of

Malononitrile with Benzaldehydes Catalyzed by 1−3

of 1 (0.01 mmol) at 30, 40, 50, and 60 °C, and the conversions

were 24%, 72%, 98%, and >99%, respectively (entries 3−6,

respectively). Noticeably, when the catalyst quantity was 0.50

mmol %, the conversion decreased to 85% (entry 7).

Therefore, the following catalytic experiments would be

carried out with 0.01 mmol of catalyst at 60 °C and reacted

for 40 min. Subsequently, we found that TIC4R (0.01 mmol)

as a basic catalyst for Knoevenagel reaction could also provide

quantitative conversion at 60 °C after 40 min (entry 8).

However, TIC4R as a homogeneous base catalyst is not easy to

recycle. Under the optimum conditions, the catalytic

conversions of 2 and 3 were both >99% (entries 9 and 10,

respectively). It can be seen that 1−3 have high catalytic

eﬃciencies for benzaldehyde and malononitrile condensations.

In addition, we have explored the reaction of benzaldehyde

with two other active methylene compounds (meldrum’s acid

and barbituric acid) (Scheme 3). For meldrum’s acid, the

conversions of 1−3 are 41%, 37%, and 24%, respectively

(

Table 3, entries 1−3, respectively). For barbituric acid, the

corresponding conversions are 55%, 44%, and 38% for 1−3,

respectively (entries 4−6, respectively). Because the molecular

sizes of meldrum’s acid and barbituric acid are larger than that

41,42

of malononitrile, the conversions decrease.

To demonstrate the general applicability of 1−3, under the

optimized conditions, a series of substituted benzaldehydes

and other types of aldehydes were used as substrates to react

with malononitrile (Table 4 and Figures S7 −S9). When

benzaldehydes substituted with electron-withdrawing groups

(

2-Cl-, 4-F-, 4-CN-, and 4-NO -) reacted with malononitrile,

conversions of >99% were obtained (entries 2−5, respec-

tively). When benzaldehyde was substituted with those

electron-donating groups, the conversions were aﬀected by

substrates. As for the 4-CH - and 2-OH-substituted groups, the

conversions of 1−3 are 98%, 97%, and 97% and 95%, 90%, and

8%, respectively (entries 6 and 7). For 4-CH CH - and 4-

2 3

OCH -substituted groups, the conversions decreased to 85%,

0%, 62%, 68%, 60%, and 48% for 1−3, respectively (entries 8

and 9). We can conclude that electron-donating substituted

groups result in lower conversions. Subsequently, several other

types of aldehydes were also used as catalytic substrates. For

hexaldelyde and 2-naphthaldehyde, high conversions of 96% to

99% were obtained for three CPs (entries 10 and 11). As for

the cinnamaldehyde, lower conversions of 76%, 64%, and 58%

were achieved, respectively (entry 12). Fortunately, crystal

samples of target products 2-(4-nitrobenzylidene)-

malononitrile and 2-(4-methoxybenzylidene)malononitrile

were isolated, and their structures were determined by

single-crystal X-ray diﬀraction (Figure S10). CPs 1−3 are

eﬀective catalysts for Knoevenagel condensations of the

substrates used. In particular, all CPs exhibit excellent catalytic

eﬃciency for the substrates with electron-withdrawing groups,

and hexaldelyde and 2-naphthaldehyde. The open channel

plays an important role in the improved catalytic eﬃciency.

Upon comparison of the catalytic eﬀects of 1−3 for diﬀerent

substrates, the results show that the catalytic eﬀects are in the

order of 1 > 2 > 3 for most types of aldehydes, which is due to

1 having a relatively large channel along the b-direction. The

substrates could easily diﬀuse into the channel and react with

the active Lewis acid sites. On the contrary, in CPs 2 and 3, the

slide of the layers made the pores smaller, and the substrate has

diﬃculty in reaching the catalytic sites. As a result, they

exhibited lower conversions. Obviously, the catalytic perform-

ances of 1−3 were aﬀected by their diﬀerent channel sizes

Figure 3. Hot ﬁltration experiments catalyzed by (a) 1, (b) 2, and (c)

after 20 min.

substrates benzaldehyde (1 mmol) and malononitrile (2

mmol) over catalyst 1 (0.01 mmol) were investigated under

diﬀerent conditions (Table 2). The study shows that only a

trace of product is produced without using any catalyst (entry

). When Zn(NO ) ·6H O (0.01 mmol) was used as the

3 2 2

catalyst, a conversion of 36% was realized (entry 2). To explore

the temperature, the reactions were carried out in the presence

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Figure 4. Recycling experiments for Knoevenagel condensation using catalysts (a) 1 , (b) 2 , and (c) 3 .

Article

Figure 6. Possible mechanism for the Knoevenagel condensation.

Figure 5. PXRD patterns of the simulated, experimental, and

activated forms of and after four cycles for catalysts (a) 1, (b) 2,

and (c) 3.

benzaldehyde and malononitrile, the three catalysts still

maintain high catalytic activities (96%, 94%, and 92%,

respectively) after four cycles. At the same time, PXRD

patterns of the separated catalysts 1 and 3 are still in good

agreement with their simulated ones (Figure 5a,c). For catalyst

2, a new peak appears at ∼12° after four cycles. Due to the

change in the solvents, the PXRD pattern of sample 2 may

change slightly (Figure 5b).

(10.3 Å × 2.4 Å, 6.3 Å × 1.9 Å, and 4.2 Å × 1.7 Å,

respectively). The larger the channels, the better the catalytic

performances.

To determine whether the catalyses are heterogeneous

reactions, we separated the catalysts at 20 min by

centrifugation, and the liquid phases were stirred for a further

0 min (Figure 3). In the prior 20 min, the conversions of CPs

−3 reached 85%, 88%, and 84%, respectively. When the

A possible mechanism for the catalysis of 1−3 has been

provided. Deprotonation of the active methylene was

−

catalysts were removed, no signiﬁcant increases were observed

for the conversions of three CPs. We demonstrated that 1−3

are heterogeneous catalysts during the Knoevenagel con-

densations.

Catalysts 1−3 were easily separated by centrifugation after

the reactions, and the cycle experiments were carried out

successively. After each run of centrifugation, the catalyst was

washed with dichloromethane and dried for the next run

enhanced by HCOO , and the Zn(II) cation interacts with

the carbonyl group of benzaldehyde. Then the carboanion

attacks the activated benzaldehyde, and benzylidenemalononi-

trile is obtained after rearrangement and dehydration (Figure

6).

To evaluate the catalytic activity of CPs 1−3, a comparison

of the conversion of benzaldehyde with malononitrile with

those of other CPs is presented in Table 5 and Table S2. The

results show that 1−3 exhibit superior catalytic capacities

(Figure 4 and Figures S11 −S13 ). For the condensation of

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

Complete contact information is available at:

Article

Table 5. Comparison of the Catalytic Activities of 1−3 with Reported CPs in Benzaldehyde and Malononitrile Reactions

catalyst

dosage/solvent

1 mmol %

temp/time

conversion (%)

ref

−3

60 °C/40 min

35 °C/6 h

50 °C/4 h

40 °C/1 h

RT/1 h

85 °C/4 h

60 °C/6 h

60 °C/1 h

60 °C/6 h

60 °C/12 h

>99

this work

Cd₃_.₅(L ) [(CH ) NH ] ·(H O) ·(H O)

3 mol %/THF

3 mmol %/ethanol

2 mol %/MeOH

18.9 mmol %/toluene

2 mol %

0.3 mmol %

2 mol %

5 mol %

[

Zn(H L )(H O) ]·3H O

Al (OH) (OCH ) (NH -bdc) ]

Co (tdc) (tpxn)

[

ZnL (H O)] ·2NO ·2DEF

Co (Hatta) (H O) ]·3DMA

Zn (TCA)(BIB)₂_.₅]·NO₃

Cd(L )(2-NH -BDC)]·DMF·0.5H O

Mn L (HL )(H O)

compared to those of several CPs. ⁴^,⁴⁴⁻⁴⁷In comparison with

the CPs with equally high conversions, 1−3 have several

advantages, such as a shorter reaction time, a smaller dosage of

Authors

Fei-Fei Wang − Key Laboratory of Polyoxometalate and

Reticular Material Chemistry, Department of Chemistry,

Northeast Normal University, Changchun 130024, People’s

Republic of China

34,48−51

catalyst, and solvent-free conditions.

Wen-Yuan Pei − Key Laboratory of Polyoxometalate and

Reticular Material Chemistry, Department of Chemistry,

Northeast Normal University, Changchun 130024, People’s

Republic of China

CONCLUSIONS

■

In summary, three two-dimensional supramolecular isomers

have been assembled by an imidazole-functionalized

resorcin[4]arene ligand and Zn ion in the presence of diﬀerent

SDAs. The isomers consist of the same Zn(II)/TIC4R ratio

and coordination modes. CP 1 displays a double-layer

structure with channels. The structures of 2 and 3 are

monolayers. The layers of 2 and 3 slide ∼4.16 and ∼6.90 Å

along the a-axis, respectively. For the Knoevenagel con-

densation, 1−3 have excellent catalytic activities and

recyclability under solvent-free condition. The catalytic

performances are in the order 1 > 2 > 3 for several type of

aldehydes. This research may provide insights for the use of

SDAs to design and synthesize CPs with diﬀerent properties.

https://pubs.acs.org/10.1021/acs.inorgchem.1c00497

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

■

This work was supported by the National Natural Science

Foundation of China (Grant 21471029).

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■

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Northeast Normal University, Changchun 130024, People’s

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