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In Situ Two-Steps Crystallization: Transformation of Kinetic into Thermodynamic Crystals Dongwon Kim, Sunghyun Park, and Ok-Sang Jung Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01916 • Publication Date (Web): 27 Feb 2019 Downloaded from http://pubs.acs.org on March 1, 2019

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Crystal Growth & Design

Crystal Growth & Design (Communication)

In Situ Two-Steps Crystallization: Transformation of Kinetic into Thermodynamic Crystals Dongwon Kim, Sunghyun Park, and Ok-Sang Jung*

Department of Chemistry, Pusan National University, Pusan 46241, Republic of Korea

Abstract: Unusual in situ two-steps crystallization on self-assembly of AgX (X- = CF3SO3- and PF6-) with 1,3,5-tris(nicotinoyloxy-methyl)benzene (L) has been carried out. The self-assembly reaction produces initial single crystals consisting of cyclophanetype 30-membered macrocyclic linked 1D coordination polymers, and then the single crystals are transformed into different morphological crystals consisting of 16membered macrocyclic linked 1D coordination polymers in the mother liquor. The crystal structures show significant difference in metallophilicity between CF3SO3- and PF6- anion.

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Development of new methodology for task-specific coordination polymers is a great challenge in the field of petrochemicals industry, anion exchanges, separation science, confined catalysis, chemo-sensors, and harmful molecules adsorption.1-11 Recent advanced synthetic methods such as photoreaction, polymorphism, anion exchange, and metal exchange, etc. have been advanced for desirable transformation of coordination frames formed via self-assembly of central metal ions as angle components with appropriate multidentate ligands as spacers.12-17 A noteworthy conceptual feature is that 1D molecular frames have easy changeability along with low entropy relative to 2D and 3D frames.18 Delicate solubility-difference of 1D may play significant role in the transformation of the products.15,19,20 In particular, some flexible tridentate ligands possessing non-innocent angle and conformational non-rigidity have produced such interesting scientific results.8,21,22 In this context, unusual in situ twosteps crystallization for 1D coordination polymerization via the self-assembly of Ag(I) ion with a flexible N-donor tridentate ligand (L) in the mother liquor will be reported. This communication reports a conceptually advanced synthetic method in self-assembly reaction. The two-steps crystallization undertook a proof-of-concept experiment using


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the flexible tridentate ligand for a delicate modulation of the coordination polymerization. Ag(I) ion has been employed as a variety of coordination geometries such as linear or T-shaped, and tetrahedral directional units.23-25 Self-assembly of AgX (X- = CF3SO3- and PF6-) with L initially affords colorless crystals of [Ag3L2] composition, and finally changes to colorless crystals of [AgL] composition in the mother liquor as shown in Scheme 1. The initial 1D coordination’s formation was attributed to the intrinsic properties of the tridentate tectonic L and the linear geometric Ag(I) ion. That is, the product formation was not significantly affected by the change of the reactants’ mole ratio and concentration. Furthermore, the initial products show the same 1D frame irrespective of anions. The most important feature is that, after about 15 days, the initial crystals, [Ag3L2], are changed to the different shape crystals consisting of [AgL] in the same mother liquor. The transformed products do not have solvate molecules, and thus are quite stable even under any aerobic condition. All crystalline products are sparingly in water and common organic solvents such as acetone, benzene, chloroform, ethyl acetate, and tetrahydrofuran, but are dissociated in strong polar solvents such as dimethyl sulfoxide, and N,N-dimethylformamide. The


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compositions and structures of all products were confirmed by elemental analyses, IR, NMR, thermal analysis, and X-ray single crystallography. The characteristic strong IR bands at 1238-1241 and 836 cm-1 (Figure S1) were found to correspond to CF3SO3- and PF6-, respectively. The thermal analyses (TGA and DSC) show that all crystals are stable up to 230 °C (Figure S2). All crystal structures are shown in Figure 1, and their crystallographic data, relevant bond lengths and angles are listed in Tables 1 and 2, respectively. The crystal structure of [Ag3L2(C4H8O)2](CF3SO3)3 is a basically 1D frame with a linear Ag(I) ion of two Ndonors and two T-shaped Ag(I) ion of two N-donors and of one O-donor from tetrahydrofuran solvate. Thus, the crystal has three silver(I) ion in an asymmetric unit. The angles of N-Ag-N including T-shape geometry is in the range of 170.9(3) – 180.0o, depending on Ag···O (2.71(1) Å from tetrahydrofuran) interactions. Each tridentate L connects two Ag(I) ions (Ag-N = 2.127(8)-2.18(1) Å) in a 30-membered ring and a Ag(I) ion in an inter-ring linker to give a linked ring 1D. The 1D interact significantly via both the face-to-face () intralayer stackings of pyridine rings (3.75 Å) and the strong Ag(I)–Ag(I) interactions (3.66 Å)26,27 to form a unique cyclophane-type structure. The


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CF3SO3- anions exist as a counteranion. The 30-membered macrocycle can be described

as

a

new

type

of

big

crown

ether.

The

skeletal

structure

of

[Ag3L2(C4H8O)2](PF6)3 is similar to the that of [Ag3L2(C4H8O)2](CF3SO3)3. The structure has one and half silver(I) ions in an asymmetric unit with linear Ag(I) and T-shaped Ag(I) of two N-donors and O-donors from tetrahydrofuran solvate. The cyclophane-type structure shows the slightly different face-to-face () intramolecular stackings of pyridine rings (3.69 Å) and the Ag(I)–Ag(I) interactions (3.71 Å). The transformed products, [AgL(CF3SO3)] and [AgL](PF6), have a basically 1D skeleton without any solvate molecules. For [AgL(CF3SO3)], there is one Ag(I) ion in an asymmetric unit, and the tridentate L connects two Ag(I) ions (Ag-N = 2.298(2) - 2.322(2) Å) in a 16membered ring and a Ag(I) ion in an inter-ring linker to give a linked ring 1D. Thus, the geometry of Ag(I) ion is a tetrahedral arrangement with the angle range of N-Ag-N = 111.1(1) –127.07(9)o. and weak interaction with the triflate anions (Ag···O = 2.576(4) and 2.577(4) Å). The 1Ds intermolecular-interact via both the face-to-face () intermolecular stackings of pyridine rings (3.40 Å for [AgL(CF3SO3)]; 3.33 Å for [AgL(PF6)]). [AgL](PF6) has a triangular Ag(I) geometry with three N-donors from Ls.


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Self-assembly of various coordination geometries of Ag(I) ions with a tridentate Ndonor ligand can principally construct 0D, 1D, 2D, and 3D skeletons, and in this case, the self-assembly reaction of Ag(I) ion with the present L initially affords colorless crystals consisting of 30-membered ring-linked 1D frameworks. A combination of the tridentate N-donor L spacer and the Ag(I) angular unit seems to contribute to the driving forces in the formation of the 1D linked ring skeleton. The tetrahydrofuran solvate molecules exist safely in skeletal units as well as in the vacancy in the crystal, implying that the pyridyl groups of L as hydrophobic aromatic walls make the molecular skeleton pliable for acceptance of the tetrahydrofuran molecules. Thus, the solvate tetrahydrofuran molecules may be partly contributed to the formation of the initial 30membered ring 1D products. For the kinetic products, the intralayer  (3.69 - 3.79 Å) and argentophilic (3.66 – 3.71 Å) interactions in the solid state may be a significant factor for the formation of the kinetic products. However, after about 15 days, the crystals consisting of the kinetic products with 30-membered ring are slowly dissociated in the mother liquor, indicating that the crystals are not so stable in the same condition. Thus, the kinetic crystals begin to be slowly transformed to form new thermodynamic


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crystals. This is an unprecedented system exhibiting an in situ two-steps crystallization in the same mother liquor. This is a unique observation in that the kinetic crystals are slowly transformed into new thermodynamic crystals. The slight solubility of the kinetic crystals including solvate molecules for a long time (> 15 days) may be an important factor for the transformation into the thermodynamic stable crystals. Furthermore, the interlayer  interaction of the thermodynamic products is stronger than that of kinetic products. The change of 30-membered into 16-membered ring of the skeletal structures may be a factor for the transformation. Thus, the stability of molecular structure seems to be a significant factor for the two-steps crystallization in the same condition. For the thermodynamic products, the coordination ability of CF3SO3- are quite different from that of PF6--28,29; the triflate acts as a coordinating anion whereas the hexafluorophosphate exists as a counteranion. In conclusion, the self-assembly of AgX (X- = CF3SO3- and PF6-) with the tridentate L produced kinetic colourless crystals consisting of 30-membered ring-linked 1Ds of [Ag3L2], and after about 15 days, the kinetic crystals are transformed into thermodynamic morphological crystals consisting of 16-membered ring-linked 1Ds in


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high yields. Thus, the self-assembly system shows an unprecedented in situ two-steps crystallization in the same mother liquor. Further experiments will provide a new detailed synthetic strategy and provide a reasonable mechanistic aspect on transformation. This system is one of unique methodological methods that may contribute to produce new conceptual molecular materials for task-specific coordination polymeric materials. Research on solubilization of some crystalline surface is undergoing.

■ ASSOCIATED CONTENT Supporting Information Experimental details. The IR spectrum of each sample (L, [Ag3L2(C4H8O)2](PF6)3, [Ag3L2(C4H8O)2](CF3SO3)3, [AgL(CF3SO3)] and [AgL](PF6). the full 1H NMR spectrum of each sample. the TGA/DSC curves of the present Ag(I) compounds, ([Ag3L2(C4H8O)2](PF6)3, [Ag3L2(C4H8O)2](CF3SO3)3, [AgL(CF3SO3)] and [AgL](PF6)), the full 13C NMR spectrum of L. This material is available free of charge via the Internet at http://pubs.acs.org. Accession Codes


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CCDC 1887156-1887159 contain 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 emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. ■ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Fax: +83-52-516-7421. Tel: +82-51-510-2591. ORCID Ok-Sang Jung: 0000-0002-7218-457X Notes The authors declare no competing financial interest. ■ ACKNOWLEDGMENT This work was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean Government [MEST] (2016R1A2B3009532 and 2016R1A5A1009405).


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Table 1. Crystallographic Data for [Ag3L2(C4H8O)2](CF3SO3)3, [AgL(CF3SO3)], [Ag3L2(C4H8O)2](PF6)3, and [AgL](PF6). [Ag3L2(C4H8O)2]-

[AgL(CF3SO3)]

[Ag3L2(C4H8O)2]-

(CF3SO3)3 C65H58Ag3F9N6O23S

formula

[AgL](PF6)

(PF6)3 C28H21AgF3N3O9S

C62H58Ag3F18N6O14 P

3

C27H21AgF6N3O6P

Mw

1881.96

740.41

1869.66

736.31

cryst system

Triclinic

Triclinic

Triclinic

Triclinic

space group

P-1

P-1

P-1

P-1

a (Å)

11.2250(4)

11.5756(7)

11.2372(2)

8.8189(4)

b (Å)

12.7772(4)

15.886(1)

12.4670(3)

10.3849(5)

c (Å)

13.6664(4)

17.113(1)

13.6800(3)

15.2505(7)

α (°)

77.411(2)

111.423(3)

76.053(1)

74.878(2)

β (°)

83.085(2)

101.407(3)

81.427(1)

83.352(2)

γ (°)

64.005(2)

101.551(4)

64.043(1)

78.492(2)

V

1718.7(1)

2740.5(3)

1670.27(6)

1318.2(1)

1

4

1

2

dcalcd (g cm3)

1.818

1.795

1.859

1.855

µ

1.047

0.882

1.048

0.906

0.0376

0.0426

0.0344

0.0247

1.920

1.036

1.034

1.037

R1 [I > 2σ(I

0.1473

0.0682

0.0927

0.0258

wR2 (all data)b

0.4536

0.1790

0.2829

0.0687

(Å3)

Z (mm1)

Rint GoF on F

2

)]a

a

R1 = Σ||Fo| – |Fc||/Σ|Fo|, bwR2 = (Σ[w(Fo2 – Fc2)2]/Σ[w(Fo2)2])1/2


16

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Table 2. Selected bond length and angle for [Ag3L2(C4H8O)2](CF3SO3)3, [AgL(CF3SO3)], [Ag3L2(C4H8O)2](PF6)3, and [AgL](PF6). [Ag3L2(C4H8O)2](CF3SO3)3

[Ag(CF3SO3)L]

[Ag3L2(C4H8O)2](PF6)3

[AgL](PF6)

Ag(1)N(1) )#1

2.132(4)

Ag(1)N(2)

2.298(2)

Ag(1N(3)

2.129(6)

Ag(1)N(1)

2.271(2)

Ag(1)N(1)

2.132(4)

Ag(1)N(3)#1

2.308(2)

Ag(1)N(3)#1

2.129(6)

Ag(1)N(2)

2.276(2)

Ag(2)N(2)

2.137(5)

Ag(1)N(1)

2.322(2)

Ag(2)N(1)

2.171(6)

Ag(1)N(3)#1

2.299(2)

Ag(2)N(3) )#2

2.148(5)

Ag(1)O(3U)

2.43(2)

Ag(2)N(2)#2

2.173(7)

N(1)Ag(1)N(2)

124.69(5)

N(1) #1Ag(1)N(1)

180.0

Ag(2)N(4)

2.310(2)

N(3Ag(1)N(3)#1

180.0

N(1)Ag(1)N(3)#1

120.53(6)

N(2)Ag(2)N(3) #2

170.9(3)

Ag(2)N(6) #2

2.313(2)

N(1Ag(2N(2)#2

174.8(3)

N(2)Ag(1)N(3)#1

114.38(6)

Ag(2)N(5)

2.321(2)

Ag(2)O(4T)

2.572(4)

N(1)Ag(1)N(3)#1

117.91(9)

N(1)Ag(1)N(2)

127.07(9)

N(3)#1Ag(1)N(2)

112.63(9)

N(1)Ag(1)O(3U)

80.6(5)

N(1)#1Ag(1)O(3U)

128.1(5)

N(1)Ag(1)O(3U)

80.7(7)

N(4)Ag(2)N(6)#2

118.36(9)

N(4)Ag(2)N(5)

125.5(1)

N(6)#2Ag(2)N(5)

111.1(1)

N(4)Ag(2)O(4T)

90.2(1)

N(6)#2Ag(2)O(4T)

120.0(1)

N(5)Ag(2)O(4T)

84.0(1)

#1

x+1, y+1, z+1

#1

x1, y, z

#1

x+2, y, z

#2

x, y+2, z+1

#2

x+1, y1, z+1

#2

x+1, y+1, z

#1

x1,y1,z1


17


Page 18 of 21

Scheme 1. Overall synthesis and procedure of in situ two-steps crystallization.


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(a) Ag2

Ag3 Ag1

(b)

(c)

(d)

Figure 1. ORTEP drawings of [Ag3L2(C4H8O)2](CF3SO3)3 (a). The structure image [Ag3L2(C4H8O)2](CF3SO3)3 ((b) top view; (c) side view), and the structure of the thermodynamic product, [AgL(CF3SO3)] (d). Solvate tetrahydrofuran molecules are designated as an space-filling mode.


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(a) Ag2

Ag3 Ag1

(b)

(c)

(d)

Figure 2. ORTEP drawings of [Ag3L2(C4H8O)2](PF6)3 (a). The structure image [Ag3L2(C4H8O)2](PF6)3 ((b) top view; (c) side view), and the structure of the thermodynamic product, [AgL](PF6) (d). Solvate tetrahydrofuran molecules are designated as an space-filling mode.


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In Situ Two-Steps Crystallization: Transformation of Kinetic into Thermodynamic Crystals Dongwon Kim, Sunghyun Park, and Ok-Sang Jung

Kinetic Ag(I) crystals of 30-membered macrocyclic linked 1D coordination polymers are transformed into thermodynamic crystals of 16-membered macrocyclic linked 1D coordination polymers in the mother liquor.


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In Situ Two-Steps Crystallization: Transformation of ... - ACS Publications

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