Synthesis and characterization of multifunctional

Journal of Organometallic Chemistry 866 (2018) 206e213

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Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem

Synthesis and characterization of multifunctional homochiral 1-D aminoacetic acid potassium metal organic framework Sasikala Vadivel a, Anna Lakshmi Muppidathi b, Kalyana Sundar Jeyaperumal a, *, Anbarasu Selvaraj c a b c

Materials Science Laboratory, Department of Physics, Periyar University, Salem, 636 011, Tamil Nadu, India Department of Physics, ERK Arts and Science College, Dharmapuri, 636 905, Tamil Nadu, India Department of Physics, Loyola College of Arts & Science, Rasipuram, 636 202, Tamil Nadu, India

a r t i c l e i n f o

a b s t r a c t

Article history: Received 16 March 2018 Received in revised form 18 April 2018 Accepted 23 April 2018 Available online 27 April 2018

The multifunctional homochiral aminoacetic acid potassium (AAAP) metal organic framework was synthesized and grown by hydrothermal technique. The structural arrangement can be described by alternating organic and inorganic layers which are constructed as 1D infinite chain along the b direction. These building blocks are cross linked further by nearest metal ions formed 1D tunnels like a framework also. Functional moieties exist in AAAP were analyzed by FT-IR spectral analysis. The optical constants like; optical band gap, absorption coefficient, extinction coefficient and refractive index were calculated using UVeViseNIR absorption spectrum. DSC study shows that compound stable upto 250 C. The dielectric constant and dielectric loss of the crystal were calculated as a function of frequency at room temperature, and the results are discussed. The piezoelectric charge coefficient (d33) and voltage coefficient (g33) were found. The nonlinear efficiency was determined by the Kurtz and Perry powder technique and the obtained value is 1.38 times that of KDP. BET analysis reveals the specific surface area of grown crystal is 104 m2/g and pore size distribution plot display the mesoporous nature. Thus, the sorption behavioral mesoporous, nonlinear and piezoelectric, AAAP act as a Multifunctional Metal Organic Framework material. © 2018 Elsevier B.V. All rights reserved.

Keywords: Multifunctional Alkali metal-based MOF Mesoporous crystals Tunnel structure Gas sensor

1. Introduction Metal Organic Frameworks (MOFs) are aberrant solid-state structures designed by sequencing [1] various atomic and/or molecular building units of metal cations and organic linkers through strong chemical bond. Functionalizing these building units and organic linkers with desired physio-chemical properties depending on the sequence enhances MOFs suitable for catalysis [2,3], fuel gas storage [4], separation [5,6], proton conducting membranes [7], tuning morphology of nanocrystals [8,9], drug delivery [10] etc. MOFs with the high surface and nano porosity are used in adsorption, purification and gas sensing [11,12] etc. alkali and alkaline earth metal-based MOFs are admired by researchers and scientists due to its, huge electronegativity, non-toxic and inexpensive regents for catalysis [13]. Potassium is the best bio-active metal cation in many biological processes [14]. Alkali metal ions

* Corresponding author. E-mail address: [email protected] (K.S. Jeyaperumal). https://doi.org/10.1016/j.jorganchem.2018.04.032 0022-328X/© 2018 Elsevier B.V. All rights reserved.

in particularly potassium cations show oxophilicity towards the carboxylate oxygens and elongate homochiral rod structure of MOFs based on naphthalimide grown under solvothermal technique using methanol [15] and alkali metal with triazole complexes were synthesized hydrothermal reaction [16]. CO2 adsorptive MOF, based on potassium and cyclodextrin was crystallized by vapor diffusion method [17]. Most of the MOFs are not stable under acidic conditions and ambient temperature [18,19]. Amino acids having carboxylic and amino groups stabilize those inconstant MOFs. Amino acids are potential organic homochiral linkers [20] with strong coordination ability, substrate binding ability [21] and modifiable nature, can distort the metal center in an organism [22]. L-thioproline (LTP) tailored the homochirality and helicity into one crystal phase during the crystallization of ZnLTP, CdLTP and NiLTP MOFs which are materialized in noncentrosymmetric chiral space groups [22]. Thermally stable and water absorbable homochiral MOF crystals containing cadmium metal units and organic linkers of Pyridine derivatives of L-leucine, L-serine, and L-threonine amino acids were hydrothermally synthesized [21]. Homochiral zeolitic

S. Vadivel et al. / Journal of Organometallic Chemistry 866 (2018) 206e213

metaleorganic frameworks based on L-alanine, D-alanine, L-serine, and L-valine combined with 5-methyltetrazole (5-Hmtz) has recently synthesized by solvothermal route line [23]. Crystals in which amino acetic acid encountered with various metal units were grown and their spectroscopic nature were studied [24e27]. Koukaras E.N. et al. (2017) have recently examined the amino acetic acid interaction with various MOFs and calculated the interaction energy of 9.8 kcal/mol [28]. A newly bio-MOF-29 Copper amino acetic acid was hydrothermally synthesized [29]. Recently a stalwart amino acetic acid functionalized MIL-53 (Fe) [30] has been synthesized in aqueous solution where amino acetic acid ameliorates the stability of MIL-53 (Fe). Amino acetic acid potassium nitrate crystals were also grown by controlled evaporation technique [31]. Hydrothermal technique was adopted to synthesize MOF crystal Cu(4,40 -bpy)1.5. NO3(H2O)1.25 [32] and other framework solids [33]. Homochiral MOF crystals based on copper and alanine derivatives have been hydrothermally synthesized [34]. One of the present endeavors centers around bringing extra functionalities into porous MOFs, for the paradigm, porous MOF based noncentrosymmetric materials [35,36]. Consequently, fuse of both NLO and piezoelectric properties into porous MOFs may prompt novel multifunctionality in the resultant materials [37]. The combination of noncentrosymmetric porous and MOF is a profoundly fascinating and testing errand [38,39]. To bring down the vitality of the framework, the symmetric data in natural motifs are probably going to transmit to the entire system [40]. Herein, we aimed to grow an amino acetic acid based potassium multifunctional metal organic framework and to investigate its structure and the intermolecular interactions by single crystal X-ray diffraction (SXRD), to study its chemical moieties by Fourier transform infrared (FTIR) and to analyze optical absorption by UVeVis NIR spectroscopic techniques. Further, it was characterized by Differential scanning calorimetry (DSC) analysis, Dielectric measurements, NLO test, Piezoelectric measurements and N2 sorption analysis to reveal its multifunctionality properties. 2. Experimental techniques 2.1. Chemicals and reagents Aminoacetic acid (Sigma Aldrich, 99% pure) and Potassium acetate (Sigma Aldrich, 99% pure) were used without further purification. 2.2. Synthesis and growth of AAAP single crystal Aminoacetic acid (1 mmol) was added with Potassium acetate (0.5 mmol) in a mixed solvent system containing ethanol and water in 1:1 M ratio. Thus, obtained solution was stirred for 3 h. The pH value of the solution was adjusted to 5 b y adding 1 M HCl. The resultant solution was transferred into the bottom of a Teflon cylinder of 25 mL capacity, placed in a stainless-steel autoclave chamber. The vacuum tight chamber was placed in an oven whose temperature was maintained at 120 C for 48 h. Then the reactor is cooled to ambient temperature at a rate of 2 C per day. The needle shaped crystals were collected in the bottom of autoclave and eroded through deionized water and dried in air.

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recorded by Bruker Tensor 27 spectrophotometer in the range 4000 to 400 cm1 by KBr pellet technique. UVeViseNIR absorption spectra were acquired in Varian Carry 5 E UVeViseNIR spectrophotometer in the range from 200 to 1200 nm. The DSC analysis of AAAP crystalline powder was carried out between 30 C and 500 C in the nitrogen atmosphere with a heating rate of 10 C/min using a SDTQ600 V8 analyzer. AAAP crystal was subjected to dielectric measurements using HIOKI 3532-50 LCR HITESTER. Piezoelectric property of the material was analyzed using OAM-DL-RS232-USB system. SHG efficiency of AAAP crystal was tested using KurtzPerry powder technique. Nitrogen adsorption-desorption isotherms were collected using Quadrasorb-evo analyzer. 3. Results and discussion 3.1. Single crystal X-ray diffraction The formula of the feature compound is (C4 H10 K1 N2 O4)n and crystallized in orthorhombic crystal system of the P212121 space group. The unit cell parameters obtained are a ¼ 5.310 (2) Å, b ¼ 8.101 (3) Å, c ¼ 17.999 (8) Å and volume is 774.3 (5) Å3. The asymmetric part of the AAAP includes amino acetic acid as one anion form (L1), and one cation form (L2) with one Potassium ion (CCDC No.1586586). Thermal ellipsoidal plot drawn using ORTEP at 60% is shown in Fig. 1. The Kþ center adopts a slightly distorted tetrahedral geometry chelated by three amino group N atoms of L2 and one amino group N atom of L1. The K-N bond length ranging from 3.316 to 3.242 Å. In AAAP MOF, alternating L2- K1-L2 units generate double zigzag bridging 1D infinite chain along the b direction. The Fig. 2 is showing the molecular packing of AAAP along b axis. The two zigzag chains are interconnected by nitrogen nodes forming “tunnels”. These tunnels (Fig. 3) have a cross sectional area of ~4 5 Å. The K ….K distance linked by L2 ligand is 5.310 Å which is high compared to recent reports of amino acid based MOFs at Potassium K(Lala) (MeOH) (4.068 Å) and KLser (4.261 Å) [41]. This kind of noncentrosymmetric open infinite tunnel MOFs as they combine porosity, more valuable in multifunctionality applications [42e44]. The hydrogen bonding interaction in AAAP inter connecting the tunnels form three dimension coordination polymer. The N atoms of L1 and L2 hydrogen bonded with three neighboring carboxylic group O2 atom of L1 atoms via N1-H3/O2#1 2.926 (5) Å, N1- H4 / O2#2 2.980 (6) Å and N2- H9/O2 #3 2.902 (5) Å. Hydrogen bonding interactions between carboxylate oxygen atoms O4 and O1 is (O4 -H7/O1 #4 2.559 (5) Å) also observed. The C1 and C2 have hydrogen bonded interactions with carboxylic group of O3 and O1 respectively (C1- H2 ⋯ O3 #5 3.083 (5), C3 - H5 ⋯ O1#6 3.246 (5)). The crystallographic data, details of data collection and the structure refinement are given in Table 1. The selected bond

2.3. Instrumentation Single Crystal X-ray Diffraction (SXRD) data were collected using Bruker-Enraf Nonius CAD4-MV31 single crystal X-ray diffractometer equipped with graphite monochromated Mo (Ka) (l ¼ 0.71073 Å) radiation. The interaction with infrared radiation was made on AAAP crystal and corresponding FTIR spectra was

Fig. 1. ORTEP view of the molecule with displacement ellipsoids drawn at 60%.

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Fig. 2. Packing arrangements of molecule.

lengths, angles and tensional geometries of AAAP are given in Table 2. The hydrogen bonding dimensions are listed in Table 3.

3.2. FTIR analysis

Fig. 3. The building of those tunnels.

Table 1 The crystallographic data and the structure refinement parameters. Empirical formula Formula weight (g/mol) Temperature (K) Wavelength (Å) Space group Cell dimension a (Å) b (Å) c (Å) Angle ( ) Volume (Å)3 Z Density g cm3 Absorption coefficient (mm1) F (000) Theta range for data collection ( ) Limiting Indices Completeness to theta % Absorbance correction Refinement method Data/parameter Goodness of fit on F2 Final R indices R1/R2 R indices (all data) WR1/WR2 Extinction coefficient Largest diff.peak and hole e Å3 Reflections collected/Unique

C2 H4 K N2 O6 191.17 293 (2) 0.7106 P 2 1 21 21 5.310 (2) 8.101 (3) 17.999 (8) a ¼ 90, b ¼ 90 g ¼ 90 774.3 (4) 4 1.640 0.677 388 3.384e25.325 6 h 5, 9 k 9, 21 l 21 99.8 Psi- scan Full-matrix least-squares on F2 142/101 1.132 0.0515/0.1550 0.0527/0.1565 0.046 (11) 0.585 and 0.480 6720/1420

The functional moieties present in the AAAP crystal and their characteristic vibration modes were studied through the recorded spectrum as shown in Fig. 4. Metallic bond with nitrogen is generally identified by its stretching vibration at 400 cm1 centered. The stretching mode of K-N bond is observed at 451 cm1. Metallic bond with NH3 makes a peak at 3200 cm1 centered [45]. The peak at 3199 cm1 attributes to the N-H group belonging to KNH3. A broad band of peaks in the region 3100-2600 cm1 are observed owing to NHþ 3 stretching but multiple combination and overtone bands shift this absorption to about 2000 cm1 [46]. The resonance at 3098 cm1 witnesses the N-H stretching. The peaks at 1647& 1569 and 896 cm1 are indicating the N-H in-plane bending and N-H out of plane bending modes. C-N bond vibrates in the range 1350e1000 cm1. The peaks at 1099, 1254 and 1309 cm1 are pertained to C-N stretching. The peak at 2740 cm1 is due to sp3 hybridization of C-H bond. The presence of carboxyl group is identified by its symmetric stretching at 1422 cm1 and asymmetric stretching at 1647 cm1. The C-C-N stretching vibration of the network is observed at 896 cm1 [47].

3.3. UVeVis NIR spectral analysis and determination of optical bandgap UVeViseNIR absorption spectra of AAAP crystal is shown in Fig. 5. The absorbance maximum is at 320 nm indicates n/p* due to the unconjugated chromophores [48]. There is no other absorption band in the visible region. The transmission is more than 80% in the entire visible and infrared region. So, the both fundamental and the second harmonic wavelength of the Nd-YAG laser can easily transmit through the material [49e52]. The optical absorption coefficient (a) depend on the photon energy (hn) helps to study the band structure and the type of transition of electrons in the crystal. The optical transmittance data have been used to evaluate optical parameters. The absorption co-efficient (a) has been taken for calculation from the transmittance spectra using the relation expressed as


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Table 2 The selected bond lengths and bond angles geometries of AAAP. Bond Angles ( )

Bond length (Å) K1N1 K1N2 O1C2 O2C2 O3C4 N2C3 C3N2 C2C1 C3C4 C4O4 C1N1

3.221 3.1209 1.2638 1.2501 1.2126 1.4735 1.4735 1.5093 1.5088 1.3003 1.4849

N1K1N2 N2K1N2 N2K1N2 N2K1N1 N2K1N2 N2K1N1 N2K1N1 N1K1N2 N2K1N2 N2K1N1 K1N2K1

78.26 111.24 99.72 150.76 103.88 97.39 78.26 78.26 103.88 97.39 79.53

K1N2C3 O1C2O2 C1C2O1 O2C2C1 C3C4O3 O3C4O4 O4C4C3 C3N2K1 C2C1N1 K1N1C1 C4C3N2

78.23 125.26 117.85 116.84 121.29 124.97 113.72 114.27 112.79 99.44 109.90

Table 3 Hydrogen-bond geometry (Å, ). D H … A

D-H

H…A

D…A

D-H…A

C1- H2…O3 C3- H5…O1 N1- H3…O2 N1- H4…O2 N2 -H9…O2 O4 -H7…O1

0.97 0.97 0.73 0.63 1.06 0.61

2.56 2.53 2.20 2.39 1.85 1.96

3.083 3.246 2.926 2.980 2.902 2.559

114 130 176 158 172 168

(5) (5) (6) (5)

(5) (5) (6) (5)

(5) (5) (5) (6) (5) (5)

(5) (5) (5) (7)

Symmetry code: (i) xþ1/2, -yþ3/2, -zþ1; (ii) -xþ1/2, -yþ2, zþ1/2; (iii) -xþ2, yþ1/2, -zþ1/2; (iv) x-1, y, z; (v) x-3/2, -yþ3/2, -zþ1; (vi) -xþ3/2, -yþ2, zþ1/2.

Fig. 5. UVeVis absorbance spectra of AAAP.

Fig. 4. FTIR spectra of AAAP.

a ¼ ð2:303=tÞ logð1=TÞ Where, T is the transmittance and t is the thickness of the title crystal. The relationship between the direct optical band gap (Eg), absorption co-efficient (a) and the incident photon energy (hn) are given by

ðahnÞ2 ¼ Aðhn EgÞ The Tauc's graph is plotted between the (ahn)2, and the photon energy (hn) is shown in Fig. 6. The value of bandgap is found to be 5.4 eV.

3.3.1. Determination of optical constants The extinction coefficient reveals the order of absorption loss when the electromagnetic wave propagates through a material. The

Fig. 6. Tauc's plot of AAAP crystal.

extinction coefficient is directly correlated to the absorption of material and absorption coefficient by following equation [53].

a ¼ 4pk=l The extinction coefficient as a function of absorption coefficient

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k ¼ al=4p The plot of extinction coefficient versus photon energy is shown in the Fig. 7.Where k is the wavelength of light. The reflectance (R) in terms of the absorption coefficient can be written as [54].

. R ¼ 1±ð1 expð atÞ þ expðatÞÞ1=2 ð1 þ expð atÞÞ The refractive index (n) can be calculated from reflectance data using the following equation [55].

n¼

1=2 2ðR 1Þ ðR þ 1Þ± 3R2 þ 10R 3

Fig. 8 shows the variation of refractive index (n) as a function of photon energy (hn). The refractive index (n) decreases with increase in wavelength reveal that grown sample absorbs at lower wavelength region. The low extinction values and higher transmittance of the grown crystal make the grown crystal more suitable for optoelectronic applications. This variation in ‘K’ and ‘n’ values with photon energy shows that the interaction takes place between photon and electrons. For AAAP crystal at k ¼ 1000 nm, the refractive index is 1.58. With the help of optical constants, the electric susceptibility (cc ) can be calculated according to the following relation [56].

So, the real and imaginary parts of dielectric constants can be calculated from the following relations

εr ¼ ðn þ ikÞ2

εr ¼ n2 k2

cc ¼ n2 k2 ε0

. 4p

Where (ε0 ) is the dielectric constant in the absence of any contribution from free carriers. The calculated value of electric susceptibility cc is 0.19 at k ¼ 1000 nm. The complex dielectric constant (ε) characterizes the optical properties of the material and is given by the following expression

εr ¼ ðn þ ikÞ2 ε ¼ n2 k2 þ 2ink ¼ εr þ iεr εr ¼ n2 k2

Fig. 7. Plot of extinction coefficient.

Fig. 8. Plot of refractive index Vs photon energy.

and

εr ¼ 2nk

At k ¼ 1000 nm, the calculated values of real (εr) and imaginary (εi) dielectric constants are 2.51 and 8.61 106 respectively.

3.4. Thermal analysis The thermogram of AAAP is shown in Fig. 9 and the compound is stable upto 250 C. The minor exothermic peak occurs at 271 C due to phase transformation peak from g to a polymorph [49]. The sharp exothermic peak at 315 C is attributed to the decomposition of ligand. The endothermic transition occurs at 334 C which involves the evolution of NH3. The sharpness of the exothermic peak shows a good degree of crystalline and after 480 C potassium starts to melt. Hence it is clear that the material is stable upto 250 C making it useful for possible application in lasers, where the crystal is desired to withstand high temperatures.

Fig. 9. Thermogram of AAAP.


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3.5. Piezoelectric (d33) measurements Piezoelectric material is the one that produces an electric charge when applied mechanical stress. In room temperature the sample is immersed in silicon oil and applied a dc poling field of 20 kV/cm1 for 30 min and applying a tapping force of 0.25 N at a tapping frequency of 110 Hz. The d33 value is found to be 8.52 pC/N which is adequately high value compared to g-Aminoacetic acid [57]. The piezoelectric voltage coefficient (g33) is also calculated [58,59], which is used for measuring the ability of the crystals to generate the amount of voltage per unit stress, and it is found to be 0.007 (Vm/N) for the grown crystal. 3.6. Dielectric studies Dielectric properties of crystal are correlated with the electrooptic property. The sample is coated with carbon paste for making electrode. The dielectric measurements have been carried out in the frequency range of 1 KHze10 MHz in ambient temperature. The variation of the dielectric constant (3 r) with increasing frequency is shown in Fig. 10. The value of εr abruptly decreases to a very low value as frequency increases because the dipoles cannot pursue the quick variations of the applied field. Such variation may be associate to the dependence of electronic, ionic, orientation and space charge polarizations. The space charge contribution will depend on the purity and perfection of the material and it has a noticeable influence in the low frequency region. The maximum value of dielectric constant (3 r) is found to be 57 at 1.0 kHz which is higher than some of the previous reported results on amino acid based materials like Amino acetic acid sodium sulphate, Amino acetic acid Phthalic acid and L-lysine L-lysinium dichloride nitrate single crystals [60e62]. The height of the peak is reduced with increasing frequencies and at 10 MHz it is diminished up to 4.31. The variations of dielectric loss with frequency are shown in Fig. 11. It is observed that the dielectric loss decreases with increasing frequency, low value (0.004 at 10 MHz) of dielectric loss suggests that the crystal has a few defects and is better for the use in photonic, electro-optic, and NLO devices etc., 3.7. Nonlinear optical characterization In NLO active crystals, the induced polarization is nonlinearly associated to the applied electric field produced by high power

Fig. 11. Dielectric loss Vs log f.

laser system. The Kurtz and Perry powder technique [63] is a highly valuable tool for initial screening of materials for second harmonic generation (SHG) which also identifies the materials as noncentrosymmetric crystal structure. For SHG testing of the material, uniform crystalline powder of 63 mm (KDP crystal in same particle size was taken as a reference material) size was packed in a microcapillary (1.5 mm diameter) tube. A Q-switched Nd:YAG laser beam of wavelength 1064 nm 10 ns pulse width with an input rate of 10 Hz was used to test the NLO property. The green emission with a wavelength of 532 nm was procured from the samples, which confirmed the SHG. The SHG efficiency of grown sample is 1.38 times that of KDP. The result is compared with other NLO materials as shown in Table 4. It is found that AAAP has high SHG compared to other materials. 3.8. Sorption properties These types of coordination polymer compounds are of particular interest in investigation of the recently exposed phenomena associated with coexistence of absorption and optical activity [67]. The porosity of crystal is calculated using crystal maker software [68]. The unit cell volume of AAAP crystal is 774.54 Å in this crystal with filled space 180.58 (23.32%) and void space 593.662 (76.68%). Void space is three times of filled space. N2 absorption isotherms were collected at 77 K and shown in Fig. 12 and the N2 absorptiondesorption isotherms and the corresponding pore size distribution are shown in Fig. 13. The obtained AAAP sample exhibits the isotherm of type IV, and the absorption branch shows an uptake of absorbed volume at low relative pressure (P/P0), which indicates the existence of mesoporous [69,70]. The AAAP pore size distribution curve displays a wide pore diameter distribution from 2.3 to 5.6 nm, and the maximum is centered at about 2.69 nm, within the range of a mesoporous (2e50 nm). At the relative pressure higher

Table 4 NLO properties of AAAP and some metal based amino acetic single crystals.

Fig. 10. Dielectric constant Vs log f.

Compound

SHG efficiency

Ref No.

KDP Amino acetic acid zinc sulphate Amino acetic acid lithium sulphate Amino acetic acid zinc chloride AAAP

1.0 0.7 0.75 0.5 1.38

Standard [64] [65] [66] Present work

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mesoporous nature of material. The specific surface area is 104 m2/ g. Hence, this novel multifunctionality AAAP material will open a new passage for the biased applications. Acknowledgements The authors Kalyana Sundar Jeyaperumal and Sasikala Vadivel thanks the UGC (Letter No. F.30-17/2014) for providing the fund through BSR Scheme. References

Fig. 12. N2 absorption-desorption isotherm of the obtained AAAP sample.

Fig. 13. AAAP pore size distribution Plot.

than 0.5, there is an increasing step of the nitrogen absorption volume. The pore volume of the obtained sample is 0.9 cm3/g, and the specific surface area is 104 m2/g. 4. Conclusion Homochiral 1-D amino acetic acid potassium tunnel as [K(NH2CH2COO) (NH3CH2COOH)]n was successfully grown by hydrothermal method. FTIR spectra of the grown crystal confirmed the various functional group of AAAP. UV cut off wavelength of grown crystal was around 320 nm and the optical band gap was found to be 5.4 eV. The absorption coefficient (a), refractive index, extinction coefficient (K) were also calculated. The thermal analysis confirms the AAAP is thermally stable upto 250 C. The dielectric studies show that the dielectric constant and dielectric loss of the crystal decreases exponentially with increase in frequency at room temperature. The piezoelectric charge coefficient d33 value was 8.52 pC/N. The nonlinear efficiency was 1.38 times higher compared to KDP. The AAAP pore size distribution curve displays a wide pore diameter distribution from 2.3 to 5.6 nm, and the maximum is centered at about 2.69 nm this reveals the

[1] H. Furukawa, K.E. Cordova, M. O'Keeffe, O.M. Yaghi, The chemistry and applications of metal-organic frameworks, Science 84 (341) (2013), https:// doi.org/10.1126/science.1230444. [2] J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Metaleorganic framework materials as catalysts, Chem. Soc. Rev. 38 (2009) 1450, https:// doi.org/10.1039/b807080f. [3] Q. Zhu, Y. Chen, W. Wang, H. Zhang, C. Ren, H. Chen, X. Chen, A sensitive biosensor for dopamine determination based on the unique catalytic chemiluminescence of metal-organic framework HKUST-1, Sensor. Actuator. B Chem. 210 (2015) 500e507, https://doi.org/10.1016/j.snb.2015.01.012. [4] A. Karmakar, C.L. Oliver, The synthesis, structure, topology and catalytic application of a novel cubane-based copper(II) metaleorganic framework derived from a flexible amido tripodal acid, Dalton Trans. 44 (2015) 10156e10165, https://doi.org/10.1039/c4dt03087g. [5] M. Fujita, S. Washizu, K. Ogura, Y.J. Kwon, Preparation, clathration ability, and catalysis of a two-dimensional square network material composed of cadmium(ii) and 4, 40 -bipyridine, J. Am. Chem. Soc. 116 (1994) 1151e1152, https://doi.org/10.1021/ja00082a055. [6] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long, Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites, Science (Wash. D C) 335 (2012) 1606e1610, https://doi.org/ 10.1126/science.1217544. [7] M. Yoon, K. Suh, S. Natarajan, K. Kim, Proton conduction in metal-organic frameworks and related modularly built porous solids, Angew. Chem. Int. Ed. 52 (2013) 2688e2700, https://doi.org/10.1002/anie.201206410. [8] M. Pang, A.J. Cairns, Y. Liu, Y. Belmabkhout, H.C. Zeng, M. Eddaoudi, Highly monodisperse MIII-based soc -MOFs (M ¼ in and Ga) with cubic and truncated cubic morphologies, J. Am. Chem. Soc. 134 (2012) 13176e13179, https:// doi.org/10.1021/ja3049282. [9] R. Vaidhyanathan, D. Bradshaw, N. Rebilly, J.P. Barrio, J.A. Gould, N.G. Berry, M.J. Rosseinsky, Zuschriften (2006) 6645e6649, https://doi.org/10.1002/ ange.200602242. [10] A. Umemura, S. Diring, S. Furukawa, H. Uehara, T. Tsuruoka, S. Kitagawa, Morphology design of porous coordination polymer crystals by coordination modulation, J. Am. Chem. Soc. 133 (2011) 15506e15513, https://doi.org/ 10.1021/ja204233q. [11] S. Achmann, G. Hagen, J. Kita, I.M. Malkowsky, C. Kiener, R. Moos, MetalOrganic frameworks for sensing applications in the gas phase, Sensors 9 (2009) 1574e1589, https://doi.org/10.3390/s90301574. [12] A.U. Czaja, N. Trukhan, U. Müller, Industrial applications of metaleorganic frameworks, Chem. Soc. Rev. 38 (2009) 1284, https://doi.org/10.1039/ b804680h. Z. Thf, Synthesis and structure of alkali metal “ ate ” complexes [13] W.J. Evans, Z.O. in the yttrium r 2, 6-dimethylphenoxide system 553 (1998) 141e148, https:// doi.org/10.1016/S0022-328X(97)00635-9. [14] S.W. Lockless, M. Zhou, R. MacKinnon, Structural and thermodynamic properties of selective ion binding in a Kþ channel, PLoS Biol. 5 (2007) 1079e1088, https://doi.org/10.1371/journal.pbio.0050121. [15] L. Wang, F. Wang, Q. Lin, Y. Kang, J. Zhang, Zeolitic Metal Organic Frameworks Based on Amino Acid, 2014, pp. 4e6, https://doi.org/10.1038/ ncomms3344. , E. Jeanneau, H. Delalu, Metal salts of the 4,5-dicyano-2H-1,2,3[16] C.M. Sabate triazole anion ([C4N5]), Dalton Trans. 41 (2012) 3817, https://doi.org/ 10.1039/c2dt12100j. [17] T.K. Yan, A. Nagai, W. Michida, K. Kusakabe, S.B. Yusup, Crystal growth of cyclodextrin-based metal-organic framework for carbon dioxide capture and separation, Proc. Eng. 148 (2016) 30e34, https://doi.org/10.1016/ j.proeng.2016.06.480. [18] D.S. Sholl, R.P. Lively, Defects in metal-organic frameworks: challenge or opportunity? J. Phys. Chem. Lett. 6 (2015) 3437e3444, https://doi.org/10.1021/ acs.jpclett.5b01135. [19] J. Canivet, A. Fateeva, Y. Guo, B. Coasne, D. Farrusseng, Water adsorption in MOFs: fundamentals and applications, Chem. Soc. Rev. 43 (2014) 5594e5617, https://doi.org/10.1039/C4CS00078A. [20] J.S. Siegel, Homochiral imperative of molecular evolution, Chirality 10 (1998) 24e27, https://doi.org/10.1002/chir.5. [21] T. Kundu, S.C. Sahoo, R. Banerjee, Variable water adsorption in amino acid derivative based homochiral metal organic frameworks, Cryst. Growth Des. 12 (2012) 4633e4640, https://doi.org/10.1021/cg3008443.

S. Vadivel et al. / Journal of Organometallic Chemistry 866 (2018) 206e213 [22] L. Dong, W. Chu, Q. Zhu, R. Huang, Three novel homochiral helical metalorganic frameworks based on amino acid ligand: syntheses, crystal structures, and properties, Cryst. Growth Des. 11 (2011) 93e99, https://doi.org/ 10.1021/cg1009175. [23] M.-Y. Li, F. Wang, Z.-G. Gu, J. Zhang, Synthesis of homochiral zeolitic metaleorganic frameworks with amino acid and tetrazolates for chiral recognition, RSC Adv. 7 (2017) 4872e4875, https://doi.org/10.1039/ C6RA27069G. [24] K. Kirubavathi, K. Selvaraju, S. Kumararaman, Growth and characterization of a new metal-organic nonlinear optical bis (thiourea) cadmium zinc chloride single crystals, Spectrochim. Acta Part a Mol. Biomol. Spectrosc. 71 (2008) 1e4, https://doi.org/10.1016/j.saa.2008.05.017. [25] T. Balu, T.R. Rajasekaran, P. Murugakoothan, Synthesis, growth and characterization of bis (glycine) lithium molybdate-A semi-organic NLO material, Spectrochim. Acta Part a Mol. Biomol. Spectrosc. 74 (2009) 955e958, https:// doi.org/10.1016/j.saa.2009.08.048. [26] S. Varalakshmi, S.M. Ravi Kumar, G. Elango, R. Ravisankar, Synthesis, growth and characterisations of semi-organic nonlinear optical crystal Amino acetic acid barium nitrate (GBN), Spectrochim. Acta Part a Mol. Biomol. Spectrosc. 133 (2014) 677e682, https://doi.org/10.1016/j.saa.2014.06.038. [27] P. Arularasan, V. Thayanithi, R. Mohan, Crystal growth, morphology, spectrographic characterization and thermal properties of Amino acetic acid Barium Bromo Chloride crystals, Spectrochim. Acta Part a Mol. Biomol. Spectrosc. 144 (2015) 8e16, https://doi.org/10.1016/j.saa.2015.01.078. [28] E.N. Koukaras, A.D. Zdetsis, G.E. Froudakis, Theoretical study of amino acid interaction with metal organic frameworks, J. Phys. Chem. Lett. 2 (2011) 272e275, https://doi.org/10.1021/jz101602p. [29] T. Sattar, M. Athar, Hydrothermal synthesis and characterization of copper glycinate ( bio-MOF-29 ) and its in vitro drugs adsorption studies, Open J. Inorg. Chem. 7 (2017) 17e27, https://doi.org/10.4236/ojic.2017.72002. [30] W. Dong, L. Yang, Y. Huang, Amino acetic acid post-synthetic modification of MIL-53(Fe) metaleorganic framework with enhanced and stable peroxidaselike activity for sensitive glucose biosensing, Talanta 167 (2017) 359e366, https://doi.org/10.1016/j.talanta.2017.02.039. [31] S. Tobin, S.G. Bubbly, S.B. Gudennavar, AIP Conf. Proc. 1349 (2011) 1297e1298. [32] O.M. Yaghi, H. Li, Hydrothermal synthesis of a metal-organic framework containing large rectangular channels, J. Am. Chem. Soc. 117 (1995) 10401e10402, https://doi.org/10.1021/ja00146a033. [33] G.X. Guan, X. Liu, Q. Yue, E.Q. Gao, Homochiral metal-organic frameworks embedding helicity based on a semirigid alanine derivative, Cryst. Growth Des. 18 (2018) 364e372, https://doi.org/10.1021/acs.cgd.7b01365. [34] C.-M. Wang, C.-H. Liao, H.-M. Kao, K.-H. Lii, Hydrothermal synthesis and characterization of [(UO2)2F8(H2O)2Zn2(4,4’-bpy)2]. (4,4’-bpy), a mixedmetal uranyl aquofluoride with a pillared layer structure, Inorg. Chem. 44 (2005) 6294e6298, https://doi.org/10.1021/ic0507060. [35] C. Wu, A. Hu, L. Zhang, W. Lin, Communication a homochiral porous metal organic framework for highly enantioselective heterogeneous asymmetric catalysis a homochiral porous metal-organic framework for highly enantioselective, Society (2005) 8940e8941, https://doi.org/10.1021/ja052431t. [36] Z. Guo, R. Cao, X. Wang, H. Li, W. Yuan, G. Wang, H. Wu, J. Li, A Multifunctional 3D Ferroelectric and NLO - Active Porous Metal - Organic Framework, vol. 131, 2009, pp. 6894e6895, https://doi.org/10.1021/ja9000129. [37] F.X. Coudert, Responsive metal-organic frameworks and framework materials: under pressure, taking the heat, in the spotlight, with friends, Chem. Mater. 27 (2015) 1905e1916, https://doi.org/10.1021/ acs.chemmater.5b00046. [38] D. Maspoch, D. Ruiz-Molina, K. Wurst, N. Domingo, M. Cavallini, F. Biscarini, J. Tejada, C. Rovira, J. Veciana, A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties, Nat. Mater. 2 (2003) 190e195, https://doi.org/10.1038/nmat834. [39] A.R. Dias, M.H. Garcia, P. Mendes, M. Fatima, M. Piedade, M.T. Duarte, M.J. Calhorda, C. Mealli, W. Wenseleers, A.W. Gerbrandij, E. Goovaerts, Organometallic nickel z II/complexes with substituted benzonitrile ligands. Synthesis, electrochemical studies and non-linear optical properties. The Xray crystal structure of [Ni(h5 C5H5) {P(C6H5)3} (NCC6H4NH2)] [PF6] 553 (1998) 115e128. [40] Y.-B. Huang, J. Liang, X.-S. Wang, R. Cao, Multifunctional metaleorganic framework catalysts: synergistic catalysis and tandem reactions, Chem. Soc. Rev. 46 (2017) 126e157, https://doi.org/10.1039/C6CS00250A. [41] D.L. Reger, A.P. Leitner, M.D. Smith, Homochiral helical metal organic frameworks of potassium, Inorg. Chem. 51 (2012) 10071e10073. [42] X.-L. Yang, M.-H. Xie, C. Zou, C.-D. Wu, Syntheses, crystal structures and optical properties of six homochiral coordination networks based on phenyl acid-amino acids, CrystEngComm 13 (2011) 6422, https://doi.org/10.1039/ c1ce05422h. [43] C. Zhuo, Y. Wen, X. Wu, Strategies to construct homochiral metaleorganic frameworks: ligands selection and practical techniques, CrystEngComm 18 (2016) 2792e2802, https://doi.org/10.1039/C5CE02593A. [44] G. An, P. Yan, J. Sun, Y. Li, X. Yao, G. Li, The racemate-to-homochiral approach to crystal engineering via chiral symmetry breaking, CrystEngComm 17 (2015) 4421e4433, https://doi.org/10.1039/C5CE00402K. [45] A.K. Brisdon, Inorganic Spectroscopic Methods, first ed., Oxford, 2005. [46] R.M. Sylvestein, Spectrometric Identification of Organic Compounds, seventh ed., Wiley, 2005.

213

[47] D.L. Pavia, G.M. Lampman, G.S. Kriz, J.R. Vyvyan, Spectroscopy, forth ed., Cengage Learning, 2007. [48] P.R. Deepthi, J. Shanthi, Optical, dielectric & ferroelectric studies on amino acids doped TGS single crystals, RSC Adv. 6 (2016) 33686e33694, https:// doi.org/10.1039/C5RA25700J. [49] S. Anbu Chudar Azhagan, S. Ganesan, Effect of zinc acetate addition on crystal growth, structural, optical, thermal properties of Amino acetic acid single crystals, Arab. J. Chem. 10 (2017) S2615eS2624, https://doi.org/10.1016/ j.arabjc.2013.09.041. ~ as, A. Ferrer-Ugalde, [50] M. Chaari, J. Cabrera-Gonz alez, Z. Kelemen, C. Vin ~ ez, Luminescence D. Choquesillo-Lazarte, A. Ben Salah, F. Teixidor, R. Nún properties of carborane-containing distyrylaromatic systems, J. Organomet. Chem. (2018), https://doi.org/10.1016/j.jorganchem.2018.03.002. [51] G.D. Batema, C.A. van Walree, G.P.M. van Klink, C. de Mello Doneg a, A. Meijerink, J. Perez-Moreno, K. Clays, G. van Koten, Octupolar organometallic Pt(II) NCN-pincer complexes; Synthesis, electronic, photophysical, and NLO properties, J. Organomet. Chem. (2018) 1e7, https://doi.org/10.1016/ j.jorganchem.2017.12.028. [52] C. Arbez-Gindre, B.R. Steele, G.A. Heropoulos, C.G. Screttas, J.E. Communal, W.J. Blau, I. Ledoux-Rak, A facile organolithium route to ferrocene-based triarylmethyl dyes with substantial near IR and NLO properties, J. Organomet. Chem. 690 (2005) 1620e1626, https://doi.org/10.1016/ j.jorganchem.2005.01.008. [53] R. Robert, C. Justin Raj, S. Krishnan, S. Jerome Das, Growth, theoretical and optical studies on potassium dihydrogen phosphate (KDP) single crystals by modified Sankaranarayanan-Ramasamy (mSR) method, Phys. B Condens. Matter 405 (2010) 20e24, https://doi.org/10.1016/j.physb.2009.08.015. [54] J. Lu, G. Shi, H. Wu, M. Wen, D. Hou, Z. Yang, F. Zhang, S. Pan, Experimental and ab initio studies of two UV nonlinear optical materials, RSC Adv. 7 (2017) 20259e20265, https://doi.org/10.1039/C7RA02027A. [55] H. Chen, P.-F. Liu, B.-X. Li, H. Lin, L.-M. Wu, X.-T. Wu, Two quaternary noncentrosymmetric chalcogenides BaAg2GeS4 and BaAg2SnS4: experimental and theoretical studies on the NLO properties, Dalton Trans. 47 (2017) 427e437, https://doi.org/10.1039/C7DT04178K. [56] R. Ashok Kumar, R. Ezhil Vizhi, N. Vijayan, D. Rajan Babu, Structural, dielectric and piezoelectric properties of nonlinear optical g-Amino acetic acid single crystals, Phys. B Condens. Matter 406 (2011) 2594e2600, https://doi.org/ 10.1016/j.physb.2011.04.001. [57] B. Moorthy, C. Baek, J.E. Wang, C.K. Jeong, S. Moon, K.-I. Park, D.K. Kim, Piezoelectric energy harvesting from a PMNePT single nanowire, RSC Adv. 7 (2017) 260e265, https://doi.org/10.1039/C6RA24688E. [58] F. Yu, Q. Lu, S. Zhang, H. Wang, X. Cheng, X. Zhao, High-performance, hightemperature piezoelectric BiB 3 O 6 crystals, J. Mater. Chem. C 3 (2015) 329e338, https://doi.org/10.1039/C4TC02112F. ski, P. Busz, Low-temperature phase transition in g-Amino acetic [59] Z. Tylczyn acid single crystal. Pyroelectric, piezoelectric, dielectric and elastic properties, Mater. Chem. Phys. 183 (2016) 254e262, https://doi.org/10.1016/ j.matchemphys.2016.08.025. [60] M. Dadsetani, A.R. Omidi, Ab initio study on optical properties of glycine sodium nitrate: a novel semiorganic nonlinear optical crystal, RSC Adv. 5 (2015) 90559e90569, https://doi.org/10.1039/C5RA14945B. [61] S. Suresh, Growth, optical, dielectric and ferroelectric properties of non-linear optical single crystal: Glycine-Phthalic acid, J. Electron. Mater. 45 (2016) 5904e5909, https://doi.org/10.1007/s11664-016-4798-5. [62] V. Vasudevan, R.R. Babu, A.R. Nelcy, G. Bhagavannarayana, K. Ramamurthi, Synthesis, growth, optical, mechanical and electrical properties of L -lysine L -lysinium dichloride nitrate ( L -LLDN ) single crystal, Bull. Mater. Sci. 34 (2011) 469e475. [63] S.K. Kurtz, T.T. Perry, A powder technique for the evaluation of nonlinear optical materials, J. Appl. Phys. 39 (1968) 3798e3813, https://doi.org/10.1063/ 1.1656857. [64] T. Balakrishnan, K. Ramamurthi, Structural, thermal and optical properties of a semiorganic nonlinear optical single crystal: glycine zinc sulphate, Spectrochim. Acta Part a Mol. Biomol. Spectrosc 68 (2007) 360e363, https:// doi.org/10.1016/j.saa.2006.12.001. [65] T. Balakrishnan, K. Ramamurthi, Growth, structural, optical, thermal and mechanical properties of glycine zinc chloride single crystal, Mater. Lett. 62 (2008) 65e68, https://doi.org/10.1016/j.matlet.2007.04.072. [66] M.R. Suresh Kumar, H.J. Ravindra, S.M. Dharmaprakash, Synthesis, crystal growth and characterization of glycine lithium sulphate, J. Cryst. Growth 306 (2007) 361e365, https://doi.org/10.1016/j.jcrysgro.2007.05.015. [67] R. Medishetty, J.K. Zare˛ ba, D. Mayer, M. Samo c, R.A. Fischer, Nonlinear optical properties, upconversion and lasing in metaleorganic frameworks, Chem. Soc. Rev. 46 (2017) 4976e5004, https://doi.org/10.1039/C7CS00162B. [68] D.C. Palmer, Visualization and analysis of crystal structures using CrystalMaker software, Z. Krist. - Cryst. Materials 230 (2015) 559e572, https:// doi.org/10.1515/zkri-2015-1869. [69] F. Zhu, P. Zhao, Q. Li, D. Yang, Synthesis and characterization of mesoporous Pd(II) organometal nanoplatelet catalyst for copper-free Sonogashira reaction in water, J. Organomet. Chem. 859 (2018) 92e98, https://doi.org/10.1016/ j.jorganchem.2018.02.004. [70] K.C. Kim, Design strategies for metal-organic frameworks selectively capturing harmful gases, J. Organomet. Chem. 854 (2018) 94e105, https:// doi.org/10.1016/j.jorganchem.2017.11.017.