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. 2023 Aug 12;13(16):2319.
doi: 10.3390/nano13162319.

Solid-State Structural Transformation in Zn(II) Metal-Organic Frameworks in a Single-Crystal-to-Single-Crystal Fashion

Jaewook An  1 , Jihye Oh  1 , Uma Kurakula  2 , Dong Hee Lee  1 , Aditya Choudhury  2 , Eunji Lee  3 , Raghavender Medishetty  2 , In-Hyeok Park  1
Affiliations

Solid-State Structural Transformation in Zn(II) Metal-Organic Frameworks in a Single-Crystal-to-Single-Crystal Fashion

Jaewook An et al. Nanomaterials (Basel). .

Abstract

Solid-state structural transformation is an interesting methodology used to prepare various metal-organic frameworks (MOFs) that are challenging to prepare in direct synthetic procedures. On the other hand, solid-state [2 + 2] photoreactions are distinctive methodologies used for light-driven solid-state transformations. Meanwhile, most of these photoreactions explored are quantitative in nature, in addition to them being stereo-selective and regio-specific in manner. In this work, we successfully synthesized two photoreactive novel binuclear Zn(II) MOFs, [Zn2(spy)2(tdc)2] (1) and [Zn2(spy)4(tdc)2] (2) (where spy = 4-styrylpyridine and tdc = 2,5-thiophenedicarboxylate) with different secondary building units. Both MOFs are interdigitated in nature and are 2D and 1D frameworks, respectively. Both the compounds showed 100% and 50% photoreaction upon UV irradiation, as estimated from the structural analysis for 1 and 2, respectively. This light-driven transformation resulted in the formation of 3D, [Zn2(rctt-ppcb)(tdc)2] (3), and 2D, [Zn2(spy)2(rctt-ppcb)(tdc)2] (4) (where rctt = regio, cis, trans, trans; ppcb = 1,3-bis(4'-pyridyl)-2,4-bis(phenyl)cyclobutane), respectively. These solid-state structural transformations were observed as an interesting post-synthetic modification. Overall, we successfully transformed novel lower-dimensional frameworks into higher-dimensional materials using a solid-state [2 + 2] photocycloaddition reaction.

Keywords: [2 + 2] photoreaction; interdigitated framework; metal–organic frameworks; single crystal to single crystal; solid-state structural transformation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Details of the formation of two Zn(II) metal–organic frameworks (blue: N atom; red: oxygen atom; orange: sulfur atom).
Figure 2
Figure 2
Crystal structure of [Zn2(spy)2(tdc)2] (1). (a) Coordination environment of Zn(II). (b) The (4,4) net formed by Zn8(tdc)4. (c) General view of 1. (d,e) Packing structures of 1. The hydrogen atoms are omitted for clarity.
Figure 2
Figure 2
Crystal structure of [Zn2(spy)2(tdc)2] (1). (a) Coordination environment of Zn(II). (b) The (4,4) net formed by Zn8(tdc)4. (c) General view of 1. (d,e) Packing structures of 1. The hydrogen atoms are omitted for clarity.
Figure 3
Figure 3
Single-crystal-to-single-crystal transformation (SCSC): the [2 + 2] cycloaddition reaction of (a) [Zn2(spy)2(tdc)2] into (b) [Zn2(rctt-ppcb)(tdc)2].
Figure 4
Figure 4
Crystal structure of [Zn2(rctt-ppcb)(tdc)2] (3). (a) Coordination environments of Zn(II). (b) pcu repeating unit of 3. (c) The (4,4) net formed by Zn8(tdc)4. (d,e) Packing structure of 3. The hydrogen atoms are omitted.
Figure 4
Figure 4
Crystal structure of [Zn2(rctt-ppcb)(tdc)2] (3). (a) Coordination environments of Zn(II). (b) pcu repeating unit of 3. (c) The (4,4) net formed by Zn8(tdc)4. (d,e) Packing structure of 3. The hydrogen atoms are omitted.
Figure 5
Figure 5
Crystal structure of [Zn2(spy)4(tdc)2] (2). (a) Coordination environment of Zn(II). (b) Top view of 2. (c) General view of 2. (d,e) Packing structure of 2. The hydrogen atoms are omitted.
Figure 5
Figure 5
Crystal structure of [Zn2(spy)4(tdc)2] (2). (a) Coordination environment of Zn(II). (b) Top view of 2. (c) General view of 2. (d,e) Packing structure of 2. The hydrogen atoms are omitted.
Figure 6
Figure 6
Single-crystal-to-single-crystal transformation (SCSC): the [2 + 2] cycloaddition reaction of (a) [Zn2(spy)4(tdc)2] into (b) [Zn2(spy)2(rctt-ppcb)(tdc)2].
Figure 7
Figure 7
Crystal structure of [Zn2(spy)2(rctt-ppcb)(tdc)2] (4). (a) Coordination environments of Zn. (b) Side view of 4. (c) The (4,4) net formed by Zn4(rctt-ppcb)2(tdc)4. (d,e) Packing structure of 4. The hydrogen atoms are omitted.
Figure 7
Figure 7
Crystal structure of [Zn2(spy)2(rctt-ppcb)(tdc)2] (4). (a) Coordination environments of Zn. (b) Side view of 4. (c) The (4,4) net formed by Zn4(rctt-ppcb)2(tdc)4. (d,e) Packing structure of 4. The hydrogen atoms are omitted.
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