Adaptive and Guest Responsive Supramolecular Porous Framework

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Adaptive and Guest Responsive Supramolecular Porous Framework: Solvent Modulated Energy Transfer towards Fingerprint Sensing Ritesh Haldar, Komal Prasad, Arpan Hazra, and Tapas Kumar Maji Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01840 • Publication Date (Web): 07 Feb 2019 Downloaded from http://pubs.acs.org on February 10, 2019

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Crystal Growth & Design

Adaptive and guest responsive supramolecular porous framework: solvent modulated energy transfer towards fingerprint sensing Ritesh Haldar,± Komal Prasad,± Arpan Hazra+ and Tapas Kumar Maji±+§* New Chemistry Unit (NCU),± Chemistry and Physics of Materials Unit (CPMU),+ School of Advanced Materials (SAMat),§ Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore-560064, India

ACS Paragon Plus Environment

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ABSTRACT. A solvent responsive, dynamic, 3D supramolecular porous host has been synthesized and structurally characterized. The structural flexibility is realized by the guest responsive structural transformation and also by the different gas and solvent vapour adsorption studies. Noncovalent encapsulation of fluorescein dye into the framework resulted dual emission through host-to-guest partial energy transfer which is utilized for solvent sensing. Diffusion of solvents modulates the structural arrangement and energy transfer.


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Introduction Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are well-known for their high crystallinity, structural modularity and versatile functionalities.1-2 Based on these features PCPs show potential applications in gas storage and separation, catalysis, drug delivery, magnetism etc.3-6 The luminescent PCPs are also very promising for molecular sensing, light harvesting, and nonlinear optical properties.7-11 Molecular recognition or sensing of metal ions, anions, volatile solvents using PCPs have been reported quite often and all those are mostly dependent on luminescence intensity from single transition (or one excited state).12-17 An easy visual readout sensing material must show a prominent shift of the emission spectra (color), or a switch on/off feature. Subtle changes in emission intensity in presence of the analyte may not strongly establish sensing efficacy. Instead a dual emissive porous material can be much more effective to fabricate an easy readout sensory material. Till date using PCPs such efforts are scarce.18-20 To synthesize a dual emissive material use of host-guest chemistry is most suitable.21-22 The requirements are a luminescent PCP with substantial porosity and an emissive dye molecule that can fit into the pores of the host PCP. Additionally, a partial energy transfer between host and the encapsulated dye may lead to a dual emissive material. A very efficient energy transfer could lead to an enhanced emission of the acceptor dye only, and will result into a single emission peak.18,

20

Considering these aforementioned conditions, we envisioned that a

PCP@dye dual emissive material, which has substantial void space even after filling the pores by guest dye molecules, can be a promising sensory material. Filling out the remaining void space by the analyte can i) bring solvatochromic shift to the both/single emission peak,23 or ii) modulate the host-to-guest energy transfer process, and change the emission intensity ratio. In


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this process, even a small change in one of the emission peak intensity can render significant emission color change in presence of a selective analyte. In this regard, flexible24 luminescent PCPs with adaptable pore structure can be ideal hosts as these can accommodate multiple guest molecules via structural modification stabilized by host-guest interactions. Adopting one of our previously established strategy,18 a luminescent 3D porous supramolecular framework based on 1D coordination chain {[Zn(ndc)(2,2′-bpy)]·2DMF)}n (1) (ndc = 2,6-naphthalenedicarboxylate; 2,2′-bpy =2,2′-bipyridine) has been synthesized as a host structure. 1 exhibited substantial structural flexibility, and encapsulation of a fluorescein (fl) dye into the supramolecular pores furnished a dual emission feature (yellow-green) (Scheme 1). Presence of void space even after dye encapsulation allowed further diffusion of various solvents, resulting tuned emission color due to structural change as well as modulation of host-to-guest energy transfer process.

Scheme 1: A supramolecular luminescent, porous framework with an encapsulated dye showing host-to-guest energy transfer and guest solvent responsive emission for fingerprint sensing.


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A solvothermal reaction of Zn(II), ndc and 2,2′-bpy produces colourless rod shaped crystals of 1. Structure determination using single crystal X-ray diffraction suggests that 1 crystalizes in monoclinic C2/c space group25 and the asymmetric unit contains one Zn(II) metal center, one ndc, one 2,2′-bpy and two guest DMF molecules. The hexa-coordinated Zn(II) metal center is coordinated by four oxygen atoms (O1A, O2A, O1A_a and O2A_a) from two carboxylate groups of ndc and two nitrogen atoms (N1 and N1_a) from one 2,2′-bpy.25 The ndc linkers connect two metal centers in bidentate mode and 2,2′-bpy binds in chelating fashion to form a 1D zigzag chain (Figure 1a). These 1D chains are held together on the ac plane through hydrogen bonding interactions between C6A-H···O2 to form a undulated 2D structure.25 These 2D layers stack along c-axis through face-to-face π···π interaction (~ 3.518 Å) between 2,2′-bpy moieties of neighbouring 1D chains (Figure 1b) that affords a 3D supramolecular framework furnishing large dumbell shaped 1D channels with dimensions 14.59 Å2 (Figure 1c).26 These channels are filled with guest DMF molecules, confirmed from thermogravimetric (TG) analysis, and elemental analysis.25 Calculated void space after removal of guest DMF molecules using PLATON software27 is 44% of the total cell volume.


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Figure 1. (a) 1D structure formed by connecting Zn(II) and ndc; (b) π-π stacking of the 2,2′-bpy from neighbouring 2D sheets along c-axis; (c) van der Waals surface added view of the dumbell shaped 1D channels along c-axis.

To assess the potential of 1 as a suitable host, we have examined its porosity and structural flexibility. The TG analysis of 1 showed release of the guest DMF molecules at 170 °C and the desolvated state (1a) is stable upto 340 °C. Interestingly, the powder X-ray diffraction (pxrd) patterns of 1a does not resemble to 1, suggesting a structural rearrangement after desolvation.25 Such change is expected as 3D framework of 1 is built up by non-covalent interactions.18 The activated 1a does not show any uptake for N2 at 77 K, possibly because of the contraction in the pore size after the guest removal.25 But at 195 K, 1a shows a step-wise uptake profile for CO2 (Figure 2a). At lower pressure (till P/P0 ~ 0.2) uptake is low, but with increasing pressure a distinct step is realized and finally uptake amount reaches to 57 mL/g. The desorption


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path creates a large hysteresis suggesting either strong interaction of CO2 with the framework or kinetic trapping. Here, the quadrupolar CO2 can interact strongly with the aromatic π rich pore surface that induce structural rearrangement during adsorption.28-30 Also for acetylene (C2H2) low pressure uptake is low (8 mL/g) and after P/P0 ~ 0.1 uptake profile rises sharply to 47 mL/g (Figure 2a). The desorption curve shows a clear hysteresis, similar to the case of CO2 desorption. Here the C2H2 molecules can interact strongly with the carboxylate oxygen and aromatic π rich pore surface, and these interactions guide the structural transformation and corresponding stepwise uptake in the framework.29,

31-32

Such stepwise uptake phenomena are commonly

observed in case of flexible framework structures.33-34 To obtain a better insight of the supramolecular pore structure we have studied methanol and benzene vapour adsorption for 1a (Figure 2b). Methanol vapour sorption isotherm shows a two-step uptake profile at 293 K; till P/P0 ~ 0.36 relative pressure a type-I profile was observed with 51 mL/g uptake which corresponds to one methanol molecule per formula. With increasing pressure uptake rises sharply to reach 115 mL/g (2.2 methanol molecules per formula) at P/P0 ~ 0.73. Another steep uptake after this pressure reaches a saturation amount of 173 mL/g which corresponds to 3.3 molecules of methanol per formula. The desorption curve creates large hysteresis with retention of ~ 1.5 molecules methanol per formula. The benzene vapour adsorption profile showed negligible uptake till P/P0 ~ 0.12, and then rises to reach final uptake amount 60 mL/g which corresponds to ~ 1.1 benzene molecules per formula (Figure 2b). Here also the desorption curve creates a distinct hysteresis which might be due to strong aromatic interactions. The gate opening type profile reiterates the flexibility in the framework and also suggest π electron rich pore surface.


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MeOH ads MeOH des C6H6 ads C6H6 des

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Figure 2. (a) CO2 and C2H2 adsorption isotherms of 1a at 195 K; (b) MeOH and C6H6 vapour adsorption isotherms of 1a at 293 and 298 K; P0 for CO2 and C2H2 are 650 and 760 Torr, respectively; P0 for MeOH and C6H6 are 12.927 and 12.601 kPa, respectively.

The absorption spectrum of 1 shows a broad feature with λmax ~ 330 nm.25 Excitation of 1 at 330 nm exhibits an emission with maximum at ~ 422 nm which can be attributed to the linker ndc emission.25 This blue emission is red shifted compared to that of noncoordinated ndc possibly due to metal coordination. Study of porosity, particularly benzene adsorption profile clearly indicates that the pore surface favors diffusion of aromatic molecules. Moreover, the framework is dynamic (flexible) and also exhibits blue emission. All these features together encouraged us to carry out dye loading experiment in 1a. We selected fluorescein (fl) dye, whose molecular size matches well with the pore size of 1 and its absorbance spectrum overlaps partially with the framework emission.25 Only 0.04 molecule of fl dye was encapsulated into the framework 1a (1a@fl) and inclusion was confirmed from 1H-NMR,25 CO2 and solvent vapour adsorption studies. Inclusion compound 1a@fl shows only ~ 20 mL/g uptake of CO2 (1/3rd the amount in 1a) which suggests decrease of void space due to dye inclusion (Figure 3a). In case of methanol vapour adsorption, the step observed at P/P0 ~ 0.36 in 1a is absent in 1a@fl and the


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total uptake amount reduced to 94 mL/g (1.9 methanol per formula), i.e nearly half of the amount in 1a (Figure 3b). Similarly, the benzene vapour uptake also reduced to half of the amount in 1a (~ 0.6 molecules per formula). The substantial amount of decrease in uptake capacity, and change in the nature of adsorption profile confirm inclusion of dye molecules inside the pores, and also indicate availability of void space for additional guest solvent inclusion.

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Figure 3. (a) CO2 adsorption isotherm of 1a@fl at 195 K; (b) MeOH and C6H6 vapour adsorption isotherms of 1a@fl at 293 and 298 K; Respective P0 values are as in Figure 2.

The absorption spectrum of 1a@fl exhibits a new peak at ~ 500 nm, attributed to the encapsulated fluorescein dye, along with framework absorbance at 330 nm.25 Excitation of 1a@fl at 330 nm shows two distinct emission bands with maxima at ~ 432 and 535 nm, which are attributed to the framework and encapsulated dye, respectively (Figure 4a). Such dual emission leads to yellow-green emission in 1a@fl (Inset Figure 4a). Direct excitation of 1a@fl at 490 nm shows comparatively low intensity emission at 535 nm which suggests energy transfer from donor framework to the fl dye (Figure 4a). Excitation spectrum of 1a@fl monitored at 550


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nm reiterates the energy transfer process.25 Further the fluorescence life time of framework in 1a@fl (~ 1.9 ns) decreases significantly compared to 1 (~ 2.8 ns) when monitored at 400 nm.25 On the other hand, monitoring the fluorescence life time of the encapsulated dye (~ 4.8 ns) at 550 nm shows subtle increase compared to that in free fluorescein (~ 4.1 ns).25 This also advocates presence of energy transfer process. However, presence of donor (host framework) emission with a decay time of ~1.9 ns suggests a partial energy transfer from framework to the fl dye. The dual emissive 1a@fl was exploited as a probe material for various solvents. Initially, 1a@fl was dispersed in solvents like methanol, acetonitrile, DMF, DMSO and benzene. Their emission spectra featured distinct I435/I535 ratios; i.e. different emission colours (Figure 4b-c). The I435/I535 ratios are 0.71 (DMF), 0.53 (methanol), 2.37 (benzene), 0.83 (DMSO), and 0.98 (acetonitrile) (Figure 4d). Such changes in emission colors in presence of different solvents of different polarity are unique in supramolecular framework systems and the dye encapsulated compound 1a@fl can be used as a fingerprint sensing material. Diffusion of the solvents into the porous matrix can be confirmed from the methanol and benzene vapour adsorption profiles as described before. Hence, the spectral change is possibly induced by the structural change upon solvent vapour diffusion. As the structure is flexible, solvents might rearrange the structure and this leads to different arrangement of fluorescein dye inside the supramolecular pores of 1a. To confirm the structural change, 1a@fl was dipped into the respective solvents (minimum amount) and PXRD patterns were collected in wet condition.25 PXRD patterns clearly suggest structural change upon solvent diffusion into the supramolecular pores and thus the energy transfer as well as emission properties are tuned.


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Figure 4. (a) Emission spectra of 1a@fl upon excitation at 330 and 490 nm; Inset: picture of 1a@fl under UV light; (b) Emission spectra of 1a@fl dispersed in different solvents upon excitation at 330 nm; (c) Photographs of 1a@fl dispersed in different solvents and upon continuous solvent vapour exposure; (d) Plot of emission intensity ratios I435/I535 observed in different solvents.

Conclusions In conclusion, a 3D supramolecular porous framework (1) from non-covalent organization of 1D coordination polymer has been synthesized. It possesses large 1D channels which contract after guest solvent removal. Dynamic nature of the framework was realized from


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CO2, C2H2 and solvent vapour adsorption studies. Benzene vapour adsorption indicates aromatic π electron rich pore surface and hence fluorescein dye could be encapsulated inside the supramolecular pores. The dye encapsulated framework shows dual emission characteristic with yellow-green color emission. Moreover, a partial energy transfer phenomenon was observed from the host framework to the guest dye. Interestingly, 1a@fl show characteristic emission when dispersed or exposed to different solvents and respective vapors like methanol, acetonitrile, DMF, DMSO and benzene leading to easy detection of each solvent. Solvent induced structural change is the most plausible factor that tunes the dual emission intensity ratios. Such type of recognition path will lead to more efficient sensing process and also novel sensory materials.

ASSOCIATED CONTENT Supporting Information. Single crystal X-ray diffraction data, and the other structural characterizations are described in the supporting information. Accession Codes CCDC 1883677 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 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 *[email protected]


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Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes Authors declare no competing financial interest. ACKNOWLEDGMENT R.H., K.P., and A.H. acknowledge Department of Science and Technology (DST), Govt. of India and JNCASR for fellowship; T.K.M. acknowledges DST (Project MR-2015/001019) and JNCASR (Project TRC-DST/ C.14.10/16-2724) for financial support.

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Table of Content

A flexible, supramolecular porous framework based on mixed linker system has been synthesized and characterized that exhibits solvent modulated host-to-guest energy transfer towards fingerprint sensing.


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Adaptive and Guest Responsive Supramolecular Porous Framework

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