Photodimerization of 1D Ladder Polymer Through Single-Crystal to

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Photodimerization of 1D Ladder Polymer Through Single-Crystal to Single-Crystal Transformation has Effect on Electrical Conductivity Sakhiul Islam, Joydeep Datta, Suvendu Maity, Basudeb Dutta, Samim Khan, Prasanta Ghosh, Partha Pratim Ray, and Mohammad Hedayetullah Mir Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00463 • Publication Date (Web): 16 May 2019 Downloaded from http://pubs.acs.org on May 18, 2019

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Crystal Growth & Design

Photodimerization of 1D Ladder Polymer Through Single-Crystal to Single-Crystal Transformation has Effect on Electrical Conductivity Sakhiul Islam,† Joydeep Datta,‡ Suvendu Maity,# Basudeb Dutta,† Samim Khan,† Prasanta Ghosh,¶ Partha Pratim Ray,*‡ and Mohammad Hedayetullah Mir*† †Department

of Chemistry, Aliah University, New Town, Kolkata 700 156, India. Email:

[email protected] ‡Department

of Physics, Jadavpur University, Jadavpur, Kolkata 700 032, India. Email:

[email protected] #Department

of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India.

¶Department

of Chemistry, R. K. M. Residential College, Narendrapur, Kolkata 700 103, India.

ABSTRACT: A one-dimensional coordination polymer (1D CP), [Cd(bpe)( p-brba)2]n (1) has been synthesized by slow diffusion method keeping the mixture of Cd(NO3)2·6H2O and 1,2bis(4-pyridyl)ethylene (bpe) ligand along with para-bromobenzoic acid (p-brba) in dark. Interestingly, the compound 1 undergoes single-crystal to single-crystal (SCSC) photochemical [2+2] cycloaddition reaction to generate dimerized 1D CP [Cd(rctt-tpcb)1/2(p-brba)2]n (2) [rctttpcb = rctt-tetrakis(4-pyridyl)cyclobutane]. As a result, π···π stacking interactions among p-brba

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ligands of adjacent chains have been removed in the dimerized product. This structural transformation has a significant effect on the conductivity of the materials.

Introduction Solid-state structural transformations through single-crystal to single-crystal (SCSC) attains an environmentally benign green concept, because it is devoid of using ecologically

harmful

organic

solvents.1-9

In

this

regard,

topochemical

[2+2]

photodimerization has attracted immense interests among the researchers working in the field of solid-state chemistry.10-14 The key factor of photodimerization reaction is to align the olefinic double bonds following the Schmidt’s criteria.15-18 This can be achieved by several factors, such as π···π stacking interaction, aurophillic and argentophillic interactions, counter anion effects etc.19-23 MacGillivray et al. developed an elegant method to align the olefinic double bonds in co-crystals for the synthesis of tailor-made cyclobutanes or ladderanes via photochemical [2+2] cycloaddition reaction.22 Vittal and co-workers employed crystal engineering principle to align olefin bond pairs in coordination polymers (CPs) for topochemical photodimerization.10 Recently, successful attempts have been made by many groups to utilize this photodimerization reaction in various potential applications.24-28 In regard to the application, we have also reported the impact of photochemical structural transformation on the electrical conductivity of a one-dimensional coordination polymer (1D CP).29 However, to establish this concept, we wanted to explore more on


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the device application using various systems. Hence, we have employed frequently used ditopic olefinic ligand 1,2-bis(4-pyridyl)ethylene (bpe) for the fabrication of CPs. Our group is mainly involved in the fabrication of 1D or 2D CPs, which would undergo supramolecular aggregations to from higher dimensional networks using monodonor pyridyl ligands projected from the frameworks.30-33 The supramolecular assembly offers a congenial environment towards charge transport through space or ‘hopping’ mechanism.33 Recently, efforts are being paid to fabricate suitable CPs, which show semiconducting behavior and Schottky diode application. As a part of our goal, herein, we are able to synthesize a 1D CP [Cd(bpe)(p-brba)2]n (1) using bpe spacer and monodentate para-bromobenzoic acid (p-brba) ligands. The 1D chains are aggregated via Br···π and π···π stacking interactions to fabricate 3D network. Interestingly, the compound 1 is photoreactive and undergoes SCSC photochemical [2+2] cycloaddition to form dimerized 1D CP [Cd(rctt-tpcb)1/2(p-brba)2]n (2) [rctt-tpcb = rctt-tetrakis(4pyridyl)cyclobutane]. Due to this solid-state structural transformation, π···π stacking interactions among p-brba ligands of adjacent chains have remained absent in the dimerized product, which leads to the reduction in electrical conductivity value after photodimerization. In our earlier study,29 we have reported that the conductivity value enhances upon photodimerization due to the increase in the extent of π···π interactions. Therefore, these results are in accordance with those observed in our reported material.


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Experimental Section Materials and methods The chemicals purchased for the synthesis were reagent grade and were used without further purification. Elemental analysis (carbon, hydrogen and nitrogen) was performed on a Perkin-Elmer 240C elemental analyzer. Infrared spectrum in KBr (4500–500 cm-1) was

recorded

using

a

Perkin-Elmer

FT-IR

spectrum

RX1

spectrometer.

Photodimerization reaction was carried out using Luzchem photoreactor (8 W UVA lamps) at ~350 nm for 30 min at room temperature. Syntheses of compounds A solution of bpe (0.036 g, 0.2 mmol) in MeOH (2 mL) was slowly and carefully layered to a solution of Cd(NO3)2·4H2O (0.062 g, 0.2 mmol), in H2O (2 mL) using 2 mL buffer solution of DMF followed by layering of H2p-brba (0. 0.040 g, 0.2 mmol) neutralized with Et3N (0.021 g, 0.2 mmol) in 2 mL EtOH. Then the resulting reaction mixture was kept in a dark cabinet. The colorless block-shaped crystals of [Cd(bpe)(p-brba)2]n, (1) were obtained after a week (0.097 g, Yield 70%). Elemental analysis (%) calcd for C26H18Br2CdN2O4: C, 44.95; H, 2.61; N, 4.03; found: C, 44.7; H, 2.4; N, 4.2. IR (KBr pellet, cm-1): 1610as(COO¯), 1391sys(COO¯). 1H NMR (300 MHz, d6-DMSO, 298K): δ = 8.59 (d, 4H, Py–H), 7.94 (d, 4H, Ph–H), 7.60 (d, 4H, Py–H), 7.54 (s, 2H, CH=CH), 7.46 (d, 4H, Ph–H). Conversion of 1 to 2: Light yellow block crystals of [Cd(rctt-tpcb)1/2(p-brba)2]n (2) were obtained by UV irradiation of crystals of 1 for 30 min. C26H18Br2CdN2O4: C, 44.95; H, 2.61; N, 4.03; found: C, 44.5; H, 2.7; N, 4.1. IR (KBr pellet, cm-1): 1585as(COO¯), 1390sys(COO¯). 1H


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NMR (300 MHz, d6-DMSO, 298K): δ = 8.34 (d, 4H, Py–H), 7.94 (d, 4H, Ph–H), 7.45 (d, 4H, Py–H), 7.23 (d, 4H, Ph–H), 4.66 (s, 2H, CH–CH). General X-ray Crystallography Single crystals of the compound 1–2 having suitable dimension, were used for data collection using a Bruker SMART APEX II diffractometer equipped with graphite-monochromated MoKα radiation (λ = 0.71073 Å). The molecular structure was solved using the SHELXT 2014/4 structure solution program.34 Least squares refinements of all reflections within the hkl range −15≤ h ≤ 15, −15≤ k ≤15, −22≤l ≤22 (1) was used to figure out the unit cell parameters and crystal-orientation matrices. The collected data (I >2σ(I)) was integrated by using SAINT program, and the absorption correction was done by SADABS.36 Non-hydrogen atoms were refined by the help of anisotropic thermal parameters. All the hydrogen atoms were placed in their geometrically perfect positions and constrained to ride on their parent atoms. The crystallographic data for 1–2 are summarized in Table S1 and selected bond lengths and bond angles are given in Table S2–S4. Device fabrication and characterization To fabricate the Schottky device, we have taken Fluorine doped tin oxide (FTO) coated glass substrates and cleaned them with 2-isopropanol, acetone and distilled water in sequence. In the meantime, we have prepared the dispersed homogeneous medium of the synthesized material and the dimethylformamide (DMF) is chosen as a medium to make the dispersed medium (as per the concentration of 4 mg/L). Then the dispersed medium is spin coated onto the FTO coated glass with 800 rpm for 2 min to produce the film. After drying the film in a vacuum chamber, the aluminum (Al) metal is deposited onto the film using the vacuum coating unit. The effective area


5


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of the fabricated devices is controlled with the help of shadow mask. We have applied a bias voltage of -1 V to +1 V to the fabricated device in ambient condition under dark and investigated its electrical properties using the Keithley 2635B sourcemeter. Theoretical Calculation Theoretical calculations were carried out via GAUSSIAN-0937 package. Here DFT-B3LYP38 hybrid functional was done. LanL2DZ basis set was assigned for all the elements present in the structural architecture. To constrain the electronic transitions time-dependent density functional theory (TDDFT)39-41 formalism of the compounds were performed. Gauss sum42 calculations were performed to calculate the fractional contribution of the coordination polymer. Results and Discussion Structural descriptions The compound 1 has been synthesized in dark by slow diffusion of bpe and p-brba in ethanol into an aqueous solution of Cd(NO3)2·6H2O and Et3N in H2O/MeOH using DMF buffer. However, the compound 2 is prepared by photochemical [2 + 2] cycloaddition reaction exposing the crystals of 1 under UV irradiation (Figure 1). X-ray crystallographic experiments reveal that 1 crystallizes in the triclinic space group P1 with Z = 2. The compound has 1D ladder polymeric structure. The asymmetric unit of 1 consists of Cd(II) centre having distorted pentagonal bipyramid geometry. The equatorial plane is described by two oxygen atoms from a chelating carboxylate group and three oxygen atoms from μ2-chelating/bridging carboxylate group (Scheme S1, Supporting Information). The axial sites are occupied by two nitrogen atoms from two


6

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bpe ligands. Here, two μ2-chelating/bridging carboxylate groups bridge a pair of Cd(II) centres to form a dinuclear [Cd2(μ2-O2CC)2] secondary building unit (SBU) such that the bpe pairs are aligned parallel with face-to-face π···π interactions (Figure S1, Supporting Information). The distance between the centre of the C=C is 3.800(7) Å in 1. A crystallographic inversion centre is present in the middle of the [Cd2(μ2-O2CC)2] ring with Cd···Cd distance of 3.8742(4) Å in 1. The SBUs are interconnected by a pair of bpe ligands to form a 1D ladder polymer (Figure 2a). Further, the 1D ladder polymer undergoes Br···π and π···π interactions to generate a three-dimensional (3D) supramolecular structure (Figure S2–S3, Supporting Information).


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Figure 1. A schematic diagram showing solid-state structural transformation of 1 to dimerized product 2. Carbon: gray; nitrogen: blue; oxygen: red; cadmium: green. The hydrogen atoms are omitted for the clarity. Here, the nonbonding distance between the double bonds of a pair of bpe ligands are congenial for photochemical [2 + 2] cycloaddition in the solid-state following the Schmidt’s criteria (< 4.2 Å). UV irradiation of single crystals of 1 for half an hour reveals the formation of 100% dimerized products as evident from 1H NMR spectra. The 1H NMR spectrum in d6-DMSO shows the complete disappearance of peak corresponding to olefinic protons (δ = 7.53) and appearance of cyclobutane protons (δ = 4.65) of rctttetrakis(4-pyridyl)cyclobutane

(Figure

S7–S8,

Supporting

Information).

Hence,

irradiated single crystal of 1 was selected for single crystal X-ray data collection. The single crystal X-ray crystallographic analysis of photodimerized product of 1, [Cd(rctttpcb)1/2(p-brba)2]n (2) exhibits the formation of a new bond across the olefinic bonds. As a result, two pyridyl rings become no more parallel and diverge from the cyclobutane ring. Therefore, Cd···Cd distance increases from 3.8742(4) Å in 1 to 4.102(1) in 2. In addition, π···π stacking interactions among p-brba ligands of adjacent chains have completely been destroyed. The centroid-centroid distance has been increased from 3.718(3) Å in 1 to 6.964–6.978 Å in 2 (Figure 2a and 2b).


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Figure 2. (a) A perspective view a part of two adjacent 1D ladder polymer of 1 (dashed lines indicate π···π interactions with the distance of 3.718(3) Å). (b) A view of a portion of two adjacent 1D polymeric chain of 2. Electrical studies We have studied the current density-voltage (J-V) characteristics of the fabricated devices under the dark condition, which are displayed in Figure 3a. Both the characteristic curves show rectifying behavior, however, the rectification ratio of compound 1 based diode is higher than that of 2. Moreover, the Ohmic conductivity of compound 1 based diode is derived as 567 times higher than the other device which is quite significant from the view of optoelectronic application. Therefore, the notable


9


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enhancement of conductivity for compound 1 has inspired us to find the parameters related to the potential ability of Schottky diode. In this regard, we have employed the thermionic emission (TE) theory to find out the device parameters.43 According to TE theory, the current density can be written as,

J = J0[exp

qVD

( ) ―1]

(1)

nKT

where,

(

𝐽0 = 𝐴𝐴 ∗ 𝑇2𝑒𝑥𝑝

―𝑞∅𝐵 𝐾𝑇

)

(2)

where J0, q, k, T, , A*, and ΦB denote the saturation current, electronic charge, Boltzmann constant, temperature, ideality factor, Richardson constant, and the potential barrier height, respectively. The Richardson constant is considered as 1.20 × 106 AK-2m-2. Here, we have adopted Cheung’s method to derive series resistance, ideality factor and barrier potential height. From TE theory, we can write the eqn. (1) according to the following manner,43 𝑑𝑉 𝑑𝑙𝑛(𝐽)

=

(𝑛𝐾𝑇𝑞) + 𝑅𝑆𝐴𝐽

(3)

where RS is the series resistance and modeled as a serially connected resistor with the diode. The consideration of series resistance impacts on the potential drop and makes a


10

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modification in the eqn. (1). Now, Cheung’s method provides a function H which can be written as,43

𝐻(𝐽) = 𝑉 ―

(𝑛𝐾𝑇𝑞)ln(𝐴 𝐽𝑇 ) = 𝑅𝑆𝐴𝐽 + 𝜂𝐵 ∗

2

(4)

Using the eqn. (3) and (4), we have plotted dV/dlnJ vs. J and H vs. J (Figure 3b and 3c). The series resistance and ideality factor are derived from the slope and intercept of dV/dlnJ vs. J plot whereas; the potential barrier height is evaluated from the intercept of H vs. J curve. The slope of H vs. J plot also provides the value of series resistance. All the diode parameters such as ideality factor, barrier height and series resistance are displayed in Table 1. The better ideality factor with lower barrier height of FTO/compound 1/Al device makes it more significant than the other device. We have analyzed the J-V characteristic using the theory of space charge limited current (SCLC). It provides us an insightful view on the charge transport mechanism in the Schottky junction. In this regard, we have plotted the J-V characteristic into semilogarithmic scale for both devices (Figure 3d). We have found three distinguished regions which correspond to different conduction mechanism governed J-V characteristics. The region-I in the low voltage regime indicates to the Ohmic conduction (J  V). The region-II which is observed in the intermediate voltage regime corresponds to the space charge limit current (SCLC) mechanism governed by shallow trapping states. Here, the current density varies as J  V2. In the region-III, the current


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density varies as J  Vn, where, n is greater than 2. This region is also influenced by the SCLC mechanism, but the exponential distribution of traps plays the major role.44

Figure 3. (a) Current-Voltage (J-V) characteristic curve of compound 1 and 2 fabricated devices (Inset: The J-V curve for FTO/compound 2/Al). dV/dlnJ vs. J and H(J) vs. J curve for (b) compound 1 and (c) 2 based Schottky diode. (d) J-V plot (semi-logarithmic) for 1 and 2 based devices. (e) I vs. V2 plot of SCLC region for the devices fabricated by compound 1 and 2.

Table 1 Schottky diode parameters of 1 and 2 Device

Ohmic

Rectification

dV/dlnJ vs. J Graph

H vs. J Graph


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fabricated by

Conductivity ()

ratio

(Sm-1)

Ideality Series Barrier Series Factor Resistance Height Resistance (η) (RS) (ϕb) (RS) (Ohm) (eV) (Ohm)

Compound 1

1.05×10-3

22.84

0.92

1.09×103

0.66

1.14×103

Compound 2

1.85×10-6

8.03

0.30

7.90×105

0.81

7.54×105

We have measured the electron mobility, transit time, SCLC conductivity and charge concentration values using the second region of J-V characteristics. According to MottGurney, the current density under the SCLC mechanism followed as,44-45 𝐽=

()

9𝜇𝑒𝑓𝑓𝜀0𝜀𝑟 𝑉2 8 𝑑3

(5)

Where, eff is the effective mobility, 0 is the permittivity of free space and 𝜀𝑟 is the dielectric constant. The value of dielectric constant is measured as 2.4 and 1.2 for compound 1 and 2, respectively (Supplementary Information). The value of eff is derived from the slope of J-V2 plot which is displayed in the Figure 3e. We have also measured transit time which signifies the time to reach from anode to cathode. The transit time (τ) of the charge carrier is derived from the following equation.44-46 The greater mobility with lower transit time of compound 1 makes the material more suitable for the optoelectronic device. 𝜏=

9𝜀0𝜀𝑟 𝑉 8𝑑 𝐽

()

(6)

We have also measured the charge concentration (N) using the following equation.46


13


N=

Page 14 of 25

σ SCLC qμeff

(7)

Where, SCLC is the SCLC conductivity. The better charge concentration of compound 1 endorses the improvement in electrical parameters found from the above studies. All the parameters of the charge transport mechanism for both the devices are enlisted in Table 2. Here, due to the solid-state structural transformation via photochemical [2+2] cycloaddition, π···π stacking interactions among the adjacent chains have been eliminated in the dimerized product. As a result, the conductivity value is significantly reduced. This observation is in good agreement with our earlier report,29 where the conductivity has been enhanced upon photodimerization due to the increase in magnitude of π···π stacking interactions. Table 2 SCLC/charge transport parameters 1 and 2 Device

SCLC Conductivity (SCLC)

N (m-3)×1017

Carrier mobility

Transit Time

μτ × 10-11

(τ) × 10-9

(m2v-1)

(Sm-1)

(μ) × 105m2v-1s-1

Compound 1

3.15×10-3

1297

7.59

9.84

15.2

Compound 2

5.74×10-6

4.58

2080

9.52

7.83

(Sec)

Theoretical studies


14

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To shed light to the semiconducting properties of the compound 1 and 2, density functional theory (DFT) computations have been performed. The semiconducting behavior is realized by the band calculation, which is normally difference between the energy of highest occupied and the lowest unoccupied molecular orbitals (E = ELUMO EHOMO, eV). Here, the theoretical band gaps of compound 1 and 2 have been calculated as 3.52 eV and 3.77 eV respectively (Figure 4), which follow the observed trend of conductivity values obtained experimentally. Thus, the electrical nature of the compounds is in well consistent with experimental findings.

Figure 4. Theoretical band gap of compound 1 and 2 calculated from DFT computation. Conclusions


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In summary, we have synthesized a Cd(II)-based ladder polymer which undergoes Br···π and π···π interactions to construct a 3D supramolecular architecture. The compound undergoes SCSC photochemical [2+2] cycloaddition reaction to generate dimerized 1D CP. Here, the structural transformation eradicates the π···π stacking interactions present among the adjacent layers. This leads to the reduction of conductivity value after photodimerization. Thus the material follows ‘box open-box close’ rule during the electrical conductivity; which may be a useful concept for material applications. SUPPORTING INFORMATION AVAILABLE Scheme S1, Figure S1-S9, Table S1-S4, FT-IR, NMR and X-ray crystallographic data in CIF format for compound 1

2. CCDC numbers 1899617-1899618. This material is

available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author To whom correspondence should be addressed. E-mails: [email protected] (P. P. R.) and [email protected] (M. H. M.) ACKNOWLEDGMENT This work was supported by SERB, India (Grant No. SB/FT/CS-185/2012) and S. I. thanks Aliah University, India for a research fellowship. J. D. thanks JU RUSA 2.0 Post


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Doctoral Fellowship Scheme for providing financial support. S. K. thanks CSIR, India, for awarding a Research Associateship (Sanction No. 09/1157 (0005) 2K19 EMR-I). P. P. R. gratefully acknowledges the financial support of this work by SERB-DST, Govt. of India (Sanction No. EMR/2016/005387, Dated 24.07.2017) REFERENCES 1. Kitagawa, S.; Uemura, K. Coordination polymers inspired by hydrogen bonds. Chem. Soc. Rev. 2005, 34, 109-119. 2. Chaudhary, A.; Mohammad, A.; Mobin, S. M. Recent Advances in Single-Crystal-toSingle-Crystal Transformation at the Discrete Molecular Level. Cryst. Growth Des. 2017, 17, 2893-2910. 3. Medishetty, R.; Koh, L. L.; Kole, G. K.; Vittal, J. J. Solid‐State Structural Transformations from 2D Interdigitated Layers to 3D Interpenetrated Structures. Angew. Chem. Int. Ed. 2011, 50, 10949-10952. 4. Kobatake, S.; Takami, S.; Muto, H.; Ishikawa, T.; Irie, M. Rapid and reversible shape changes of molecular crystals on photoirradiation. Nature 2007, 446, 778-781. 5. Vittal, J. J. Supramolecular structural transformations involving coordination polymers in the solid state. Coord. Chem. Rev. 2007, 251, 1781-1795. 6. Kole, G. K.; Vittal, J. J. Crystal Engineering of Topochemical Solid State Reactions. Chem. Soc. Rev. 2013, 42, 1755−1775. 7. Wang, X.-P.; Chen, W.-M.; Qi, H; Li, X.-Y.; Rajnák, R.; Feng, Z.-Y.; Kurmoo, M.; Boča, R.; Jia, C.-J.; Tung, C.-H.; Sun, D. Solvent-Controlled Phase Transition of a CoII-Organic


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Single-crystal to single-crystal structural transformation of 1D coordination polymer (CP) to dimerized 1D CP, which impacts the electrical conductivity and Schottky nature of the material.


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Single-crystal to single-crystal structural transformation of 1D coordination polymer (CP) to dimerized 1D CP, which impacts the electrical conductivity and Schottky nature of the material.


Photodimerization of 1D Ladder Polymer Through Single-Crystal to

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