Water mediated proton conductance in a hydrogen-bonded Ni(II)-Bipyridine-glycoluril chloride self-assembled framework
Sakharam B. Tayade,[a] Satish S. Bhat,[a] Rajith lllathvalappil,[b],[c] Vishal M. Dhavale,
[b],[c],[d] Vitthal A. Kawade,[a] Avinash S. Kumbhar,*,[a] Sreekumar Kurungot,[b],[c]
Christian Nather[e]
aDepartment of Chemistry, Savitribai Phule Pune University, Pune-411007, IndiabPhysical and Materials Chemistry Division, National Chemical Laboratory, Pune-411008, IndiacAcademy of Scientific and Innovative Research (AcSIR), Anusandhan Bhavan, 2 Rafi Marg, New Delhi-110001, IndiadInorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hydrabad-500 007, IndiaeInstitute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth-Str.2, 24118 Kiel, Germany
CONTENTSection I: Experimental Details a) Synthesis of Bipyridine Glycoluril (BPG) LigandSection II: Single Crystal X-ray Data Refinement Parameters for [Ni(BPG)3]Cl2
.12H2OSection III: Packing diagrams of [Ni(BPG)3]Cl2
.12H2OSection IV: Thermogravimetric analysis of [Ni(BPG)3]Cl2
.12H2OSection V: IR Spectroscopy of [Ni(BPG)3]Cl2
.12H2OSection VI: Gas Adsorption Isotherms of [Ni(BPG)3]Cl2
.12H2OSection VII: Proton Conductance Studies of [Ni(BPG)3]Cl2
a) Synthesis of bipyridine glycoluril (BPG): Condensation reaction of 1,10-phenanthroline-5,6-dione (0.5 g, 2.38 mmol) and urea (0.35 g, 5.83 mmol) in methanol with trifluoroacetic acid (2.71 g, 23.78 mmol) yielded 60% of BPG, as an insoluble white powder, which was isolated, washed with water and diethyl ether, and then dried in vacuum.Yield: 60 %; elemental analysis calcd. for C14H10N6O2·2H2O: C, 50.86; H, 4.27; N, 25.44%; Found: C, 51.54; H, 4.33; N, 25.75%; 1H-NMR (DMSO-d6, room temperature, ppm): δ = 8.72 (d, 2H), 8.31 (s, 4H), 8.06 (d, H), 7.54 (dd, 2H); I.R. (KBr, cm-1): C=O (1695), N-H (3209), O-H (3418), C=N (1581), C=C (1450); mp ˃330 °C.
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Section II: X-ray crystallographic data
Table S1. X-ray crystallographic data and refinement parameters for compound 1
Molecular Formula [Ni(BPG)3]Cl2 .12H2O
Empirical formula C42H54Cl2N18NiO18Formula weight 1228.64Temperature 170(2) KWavelength 0.71073 ÅCrystal system monoclinicSpace group P21/cUnit cell dimensions a = 20.9377(11) Å α = 90°
b = 12.3747(6) Å β = 100.209(6)°
c = 40.8557(19) Å γ = 90°
Volume 10418.0(9) Å3
Z 8Density (calculated) 1.567 Mg/m3
Absorption coefficient 0.567 mm-1
F(000) 5104Crystal size 0.4 × 0.3 × 0.3 mm3
Theta range for data collection 1.72 to 20.89°.Index ranges -20<=h<=20, -12<=k<=12, -40<=l<=37Reflections collected 30347Independent reflections 10870 [R(int) = 0.0315]Completeness to theta = 20.89° 98.5 % Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 10870 / 0 / 1457Goodness-of-fit on F2
1.016Final R indices [I>2sigma(I)] R1 = 0.0437, wR2 = 0.1194R indices (all data) R1 = 0.0571, wR2 = 0.1281Extinction coefficient 0.00045(12)Largest diff. peak and hole 0.583 and -0.590 e.Å-3
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Table S2. Selected bond lengths [Å] and angles [°] for compound 1
Section III: Crystal structure and packing diagrams of compound 1.
Fig. S1 (a) Crystal structure of the two crystallographically independent molecules in 1, with labeling and displacement ellipsoids drawn at the 50% probability level. (b) Glycoluril groups of the building unit forming hydrogen-bonding with the neighboring water molecules.
(a)
(b)
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Fig. S2 Viewed along crystallographic b axis of compound 1 showing (a) continuous zigzag chain of water molecules (Colour codes: Oxygen red, Chloride green and Nickel as purple) and (b) 3D supramolecular framework with the channels filled with H2O and Cl anions. (Colour codes: Oxygen red, Chloride green and Nickel as violet).
Section IV: Thermogravimetric analysis of compound 1
(a)
(b)
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Fig. S3 Thermogravimetric analysis of 1 under N2 atmosphere showing weight loss steps.
Section V: IR spectroscopy of compound 1
Fig. S4 IR spectra showing reversible hydration and dehydration of 1.
Section VI: Gas adsorption isotherms of compound 1
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Fig. S5 N2 adsorption isotherm for 1 at 77 K.
Fig. S6 H2 adsorption isotherm for 1 at 77 K.
Section VII: Proton conductance studies of compound 1
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Impedance measurement has been carried out using following set up, for the analysis of compound 1 (i. e. sample 1) pellet size 1.3 cm in diameter and 0.10 cm in thickness has been used.
Fig. S7 Showing the set up used for the proton conductivity measurement (Pellet of compound 1 sandwiched between two stainless steel electrodes).
The proton conductance of compound 1 was determined by using the equation;
σ = l / (R×A)
Where, σ = proton conductivity (Scm-1), l = pellet thickness (cm), R = resistance of the pellet (Ω) A = area of the pellet (cm2).
Resistance values obtained by using following equivalent circuits:
Where, Q1 and Q2 = Constant phase element, R1 and R2 = Resistance
Compound 1 in theform of pelletElectrodes
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10000 20000 30000 40000 50000 60000 70000
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-Z''/
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30 C
Fig. S8 Nyquist plot of conductance for 1 at 30 °C, 95 % RH
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-Z''/
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40 C
Fig. S9 Nyquist plot of conductance for 1 at 40 °C, 95 % RH
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4000 8000 12000 16000 20000 24000
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-Z''/
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50 C
Fig. S10 Nyquist plot of conductance for 1 at 50 °C, 95 % RH
Fig. S11 Nyquist plot of conductance for 1 at 60 °C, 95 % RH
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60 C
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Z'/
70 C
Fig. S12 Nyquist plot of conductance for 1 at 70 °C, 95 % RH.
1000 1500 2000 2500 3000 3500 4000
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-Z''/
Z'/
80 C
Fig. S13 Nyquist plot of conductance for 1 at 80 °C, 95 % RH.
Reproducibilty of proton conductance in compound 1
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For the analysis pellet diameter 1.3 cm and thickness 0.094 cm (sample 2), 0.082 cm (sample 3) and 0.13 cm (sample 4) have been used.
Fig. S14 (a) Comparision of Nyquist plots of the samples 1, 2, 3, and 4 at 95 °C, 95% RH. (b) Proton conductance variation in samples 1, 2, 3 and 4 at 95 °C, 95% RH.
Table S5. Proton conductance comparison of compound 1 with other proton conductors.
(a)
(b)
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a) Comparison of proton conductance of Compound 1 with Hydrogen-Bonded Frameworks
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