The effect of metalation processes on polymer morphology and conductivity properties

Abstract

In this work, an insoluble three dimensional (3D) porous polymeric structure and their metal complexes were synthesised by the condensation reactions of meta(m)-phenylenediamine, para(p)-phenylenediamine and glutaraldehyde. The morphological and spectral features of the porous polymeric structures were determined using different analytical and spectroscopic methods, including field emission scanning electron microscopy, four-point probe electrical conductivity, photoluminescence spectroscopy, Fourier-transform infrared spectroscopy, surface area Brunauer–Emmett–Teller and magnetic and thermal behaviours. According to the obtained data, the shape, size and photoluminescence properties of the compounds, especially the conductivity, were clearly changed after the metalation processes.

Keywords

Coordination polymers electrical conductivity luminescence measurements

Introduction

Technological development and an increasing human population increase energy consumption rates. Fossil fuel–based energy sources create the emission of carbon dioxide in the atmosphere, which causes global warming. The increase in green gas emissions in the atmosphere is warning us to decrease carbon dioxide emissions through more environmentally friendly solutions.^1–3 One of the most likely solutions for solving this problem is the improvement of electric-based technologies.^4,5 Electrical vehicles, such as electric cars and smart portable devices, need an advanced energy storage system for high efficiency.⁶ Upon those demands for energy storage systems, the progression of battery technologies with power density, long life cycles, high-energy density and low costs has become one of the hottest topics for many research groups. Lithium (Li-ion) rechargeable batteries are one of the most important and likely solutions for the new generation of energy storage systems.⁶ However, morphological reconstruction after cycling of a battery causes new architectural structures of morphology, such as dendrite shapes that make a Li-ion battery inactive and responsible for short circuits.^7–9 To figure out the deterioration of the battery’s performance dependent on the surface fractures, the surface of the battery should be protected with solid electrodes. Transition metal oxide, porous carbon and conductive polymers have been widely investigated as solid electrodes to protect the battery’s surface from fractures.^8,10,11 Conductive polymers are one of the best potential materials for protection of the Li battery surfaces.^12–17 The morphological features of the polymers and their production methods, the number of donor atoms and centres, the kind of metals and their ionic charge, the hydrogen bond and the π-π stacking in the polymer and the steric hindrance are crucial for designing well-tuned and stable electrodes.^14,18–22 More specifically, the type of organic linker in the polymer is also one of the most significant points to achieve a targeted, efficient porous morphology because linker ligands, having a single C–C bond (sp³) and donor group, have the ability to give flexibility to each of the polymeric units.^6,23–27 Therefore, the coordination polymers can rotate around the flexible linkers. The morphology of the molecules in the polymeric structure can grow in different directions.^26,28-34 The 3D structure, the porosity of the coordination polymers and the conductivity are highly effective for application, such as in a flexible electrode for new generation battery technologies.^35–37 Polymers, such as polyaniline (PANI) and polypyroline (PPy), have been used as electrodes for enhancing the cycling stability and lifetime, but the swelling and shrinking of the polymeric structure after the charge and discharge of the battery deteriorates the polymer’s performance.^9,38,39 For this purpose, the beneficial modification of conductive polymers with some transition metals, Ni, Co, and Cu, plays a vital role in structural-electrochemical stability and conductivity.^{13,17,39–41} The transition metals contribute to the capability of the battery’s capacity by providing a high number of transferred electrons as intercalation. Furthermore, the production of the coordination polymers with the transition metals enables the fast charging of a battery and improves the stable-cycling number. Our previous experiences showed that the preparation of the coordination polymers containing N and O donor atoms allows for the tuning of porous structures depending on the preparation methods. ^35,36,42 In addition to the methods, the type of monomeric unit, preparation method and metalation process play a key role in the behaviour of the polymer.^43–47 The monomeric units as linkers are one of the most important cases for achieving targeted compositions because of electrical conductivity and a 3D structure. If the linker has double bonds that allows the delocalisation of electron, then the conductivity rises. However, the linker, including the longer carbon chain, exhibits unconventional behaviours that mitigates the conductivity but develops the 3D structures. Therefore, we believe that this work sheds light on the effective parameters for the designing of new functionalised polymeric structures for different applications.

In this study, we present the production of imine-based polymers and their morphological, electrical and photoluminescent properties after the metalation processes. The produced compounds were characterised through elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), inductively coupled plasma (ICP), field emission scanning electron microscopy (FESEM), four-point probe conductivity (FPP), Brunauer–Emmett–Teller (BET), powder X-ray diffraction (PXRD) analysis, luminescent properties and magnetic susceptibility measurements. The results showed that the conductivity behaviours significantly changed after the metalation processes. Furthermore, the linkers play an important role in producing different 3D morphological and surface structures. This unique application opens new pathways for tuning a polymeric structure in the production of advanced materials.

Experiment

Materials

p- and m-phenylenediamine, glutaraldehyde (25% water solution), CoCl₂.6H₂O, NiCl₂.6H₂O, CuCl₂.2H₂O, ethanol, methanol and dichloromethane were commercially purchased. The pH values of the reactions were measured using the Hanna 211 pH metre. The infrared spectra were obtained on a Perkin-Elmer RX-1 (Potassium Bromide [KBr] disk; 4000–400 cm⁻¹) FT-IR spectrometer. The surface morphologies of the compounds were determined by Carl Zeiss, SUPRA-55. The TGA was performed with a Perkin-Elmer Pyris Diamond TG/DTA N₂ (30–900°C) at a heating rate of 10°C/min. A Perkin-Elmer Optima 2100 DV ICP-OES instrument was used for the ICP analysis. A Rigaku MiniFlex system with CuKα radiation (λ = 1.54,059 Å) was used for the PXRD studies. The single-photon fluorescence spectra of the compounds were collected on a Perkin-Elmer LS55 luminescence spectrometer. The magnetic susceptibility measurements were performed by using Sherwood Scientific magnetic susceptibility. The FPP electrical conductivity device and manual hydraulic pressure of 20,000.0 kg/cm² was used. The melting point of the produced materials was measured using the melting point apparatus B450 Buchi.

Methods

Synthesis of polymeric ligands

The polymeric ligands were prepared by the refluxing of (1.081 g, 10 mmol) for p-phenylenediamine and (1.081 g, 10 mmol) for m-phenylenediamine with corresponding glutaraldehyde (4.005 g in water solution, 10 mmol) in methanol (50 mL) for 3 h. The dark brown solution was filtered, and an insoluble solid was washed three times with 20 mL methanol. The produced polymer and metal complexes were dried under a 20-mbar vacuum for 12 h. The yields were calculated as 91.5% for P-1 and 94.6% for P-2, respectively (Figure 1) (P-1): Colour: light brown. Melting point (MP): <300^°C. Anal. Calcd. For C₁₂H₁₄N₂: C, 75.82; H, 8.10; N, 16.08. Found: C, 75.73; H, 7.64; N, 15.52%. FT-IR (KBr pellet, cm⁻¹): 3442–3342 υ(O-H) aromatic or water, 2942 υ(C-H) aliphatic, 1615 υ(CH = N), 1497 υ(C–C) aromatic.

Figure 1.

The structure of the polymeric ligands and the predicted metal complexes.

(P-2): Colour: dark brown. MP: <300^°C. Anal. Calcd. For C₁₂H₁₄N₂: C, 75.82; H, 8.10; N, 16.08. Found: C, 76.04; H, 8.17; N, 15.45%. FT-IR (KBr pellet, cm⁻¹): 3335 υ(O-H) aromatic or water, 2930 υ(C-H) aliphatic, 1656 υ(CH = N), 1505 υ(C–C) aromatic.

Synthesis of polymeric complexes

The polymeric complexes were prepared using the following template technique: p-phenylenediamine (1.081 g, 10 mmol) or m-phenylenediamine (1.081 g, 10 mmol) were dissolved in methanol (30 mL) at room temperature. After the dissociation of the monomer was completed, the metal salt was added to the solution. An appropriate amount of metal salt (0.238 g, 1 mmol) for CoCl₂.6H₂O; (0.237 g, 1 mmol), for NiCl₂.6H₂O; (0.170 g, 1 mmol) and for CuCl₂.2H₂O was dissolved in CH₃OH (20 mL) and added to the monomers solution. These reaction mixtures were heated under reflux for 1 h; the glutaraldehyde was added (4.005 g from 25% water solution, 10 mmol) in the reaction medium; and they were boiled for 3 hours. All of the polymeric metal complexes were collected by filtration, washed with MeOH and dried under a vacuum for 12 h (Figure 1).

(P¹-Cu): Yield: 89.6%, Colour: dark brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₃Cl₂N₂Cu: C, 42.94; H, 4.26; Cl, 21.97; Cu, 20.65; N, 9.10%; found: C, 41.60; H, 4.81; Cl, 19.56; Cu, 15.69; N, 8.60%. FT-IR (KBr pellet, cm⁻¹): 3434 and 3314 υ(O-H) water, 2960 υ(C-H) aliphatic, 1614 υ(CH = N), 1527 υ(C–C) aromatic, 583 υ(Cu-N).

(P¹-Co): Yield: 93.9%, Colour: dark brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₇Cl₂N₂O₂Co: C, 38.96; H, 5.05; Cl, 20.91; Co, 17.38; N, 8.26%; found: C, 40.90; H, 5.23; Cl, 18.94; Co, 15.12; N, 8.03%. FT-IR (KBr pellet, cm⁻¹): 3549 and 3330 υ(O-H) water, 2942 υ(C-H) aliphatic, 1611 υ(CH = N), 1498 υ(C–C) aromatic, 690 υ(Co-N).

(P¹-Ni): Yield: 92.4%, Colour: Brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₇Cl₂N₂O₂Ni: C, 38.99; H, 5.06; Cl, 20.92; Ni, 17.32; N, 8.27%; found: C, 40.37; H, 5.31; Cl, 19.76; Ni, 16.25; N, 7.51%. FT-IR (KBr pellet, cm⁻¹): 3320–3218 υ(O-H) water, 2930–2832 υ(C-H) aliphatic, 1610 υ(CH = N), 1497 υ(C–C) aromatic, 590 υ(Ni-N).

(P²-Cu): Yield: 91.7%, Colour: Brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₃Cl₂N₂Cu: C, 42.94; H, 4.26; Cl, 21.97; Cu, 20.65; N, 9.10%; found: C, 40.89; H, 5.04; Cl, 19.56; Cu, 15.69; N, 8.37%. FT-IR (KBr pellet, cm⁻¹): 3438 and 3317 υ(O-H) water, 2970 υ(C-H) aliphatic, 1610 υ(CH = N), 1505 υ(C–C) aromatic, 618 υ(Cu-N).

(P²-Co): Yield: 91.2%, Colour: dark brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₇Cl₂N₂O₂Co: C, 38.96; H, 5.05; Cl, 20.91; Co, 17.38; N, 8.26%; found: C, 40.43; H, 5.41; Cl, 18.94; Co, 15.12; N, 7.15%. FT-IR (KBr pellet, cm⁻¹): 3308 and 3240 υ(O-H) water, 2957 υ(C-H) aliphatic, 1601 υ(CH = N), 1506 υ(C–C) aromatic, 680 υ(Co-N).

(P²-Ni): Yield: 90.8%, Colour: brown. MP: >300^°C. Anal. Calcd. For C₁₁H₁₇Cl₂N₂O₂Ni: C, 38.99; H, 5.06; Cl, 20.92; Ni, 17.32; N, 8.27%; found: C, 40.28; H, 6.02; Cl, 19.76; Ni, 16.25; N, 8.49%. FT-IR (KBr pellet, cm⁻¹): 3299–3248 υ(O-H) water, 2940 υ(C-H) aliphatic, 1600 υ(CH = N), 1516 υ(C–C) aromatic, 624 υ(Ni-N).

Results and discussion

The physical and analytical properties of all the compounds were summarised in Table 1. According to the obtained elemental analysis data, the amount of the calculated hydrogen is lower than the theoretical calculation results. They overlapped with the TG/DTA results because of water molecules on the porous morphological structure or in the nano sized channel. As a consequence of the adsorbed water on the porous polymers, the other elements, such as C and N, have a lower value than the theoretical calculations. One other reason may concern the molecular structure of the polymer having a low coordination number; hence, the transition metals coordinated less than the theoretical calculation. The melting point of all the polymers and metal complexes was higher than 300^°C.

Table 1.

The ICP, elemental analysis and reaction yields of the compounds.

Compounds	Yield %	% Metal (ICP)	% Elemental Analysis
Compounds	Yield %	M_Cal./M_Found	C_Cal./C_Found	H_Cal./H_Found	N_Cal./N_Found
P ¹	91.5	—	75.82/75.73	8.10/7.64	16.08/15.52
P ¹ -Co	93.9	17.32/16.08	38.96/40.90	5.05/5.23	8.26/8.03
P ¹ -Ni	92.4	17.41/16.03	38.99/40.37	5.06/5.31	8.27/7.51
P ¹ -Cu	89.6	17.38/16.20	42.94/41.60	4.26/4.81	9.10/8.60
P ²	94.6	—	75.82/76.04	8.10/8.17	16.08/15.45
P ² -Co	91.2	17.32/16.48	38.96/40.43	5.05/5.41	8.26/7.15
P ² -Ni	90.8	17.32/16.48	38.99/40.28	5.06/6.02	8.27/8.49
P ² -Cu	91.7	17.38/15.28	42.94/40.89	4.26/5.04	9.10/8.37

*Cal: Calculated.

ICP: Inductively coupled plasma.

FT-IR Spectra

The FT-IR spectra of the polymeric ligands and their complexes are presented in Table 2 and Supplementary Figures S1–S8. A strong and broad absorption band at 1656 cm⁻¹ for P² and 1615 cm⁻¹ for P¹, as shown by the ligands, is attributable to the υ(C = N) stretching. In all the complexes, this band shifted the lower frequencies, indicating the coordination of azomethine nitrogen to the metal.^44,48 The donation of electrons through the azomethine nitrogen diminishes the (C = N) bond electron density, and hence, the υ(C = N) stretching shift of the lower frequencies. This is supported by the appearance of a new band in the 583–690 cm⁻¹ region due to the metal ligand bonding.⁴³ The broad absorption bands relative to the υ(O-H) stretching bands in the range of 3549–3218 cm⁻¹ are attributed to the coordination of water to metal for the polymeric metal complexes.

Table 2.

FT-IR spectral bands (cm⁻¹) and the magnetic susceptibility values of the compounds.

Compound	υ(OH)	υ(C = N)	υ(M-N)	M _eff (B.M.)	n
P ¹	3442–3342	1615	—	—	—
P ¹ -Cu	3434–3314	1614	583	1.91	1
P ¹ -Co	3549–3330	1611	690	5.19	3
P ¹ -Ni	3320–3218	1610	590	2.77	2
P ²	3335	1656	—	—	—
P ² -Cu	3438–3317	1610	618	1.97	1
P ² -Co	3308–3240	1601	680	4.36	3
P ² -Ni	3299–3248	1600	624	3.34	2

Magnetic properties of the complexes

According to the magnetic moment results (Table 2), the complex (P¹-Cu) and (P²-Cu) have tetrahedral or square planar geometry, but the other complexes (P¹-Co), (P¹-Ni), (P²-Co) and (P²-Ni) have octahedral geometries. The experimental μ_eff values for the polymeric complexes are within the range found for the polymeric complexes d⁹ for [(Cu(P¹)Cl₂].2H₂O (P¹-Cu), d⁷ for [Co(P¹)Cl₂(H₂O)₂] (P²-Cu), d⁸ for [Ni(P¹)Cl₂(H₂O)₂] (P¹-Ni), d⁹ for [Cu(P²)Cl₂].2H₂O] (P²-Cu), d⁷ for [Co(P²)Cl₂(H₂O)₂] (P²-Co) and d⁸ for [Ni(P²)Cl₂(H₂O)₂] (P²-Ni).

Thermogravimetric analysis

The TG/DTA curves of the compounds and explanations are given in Supplementary Figures S5–S7 in the supplementary data. The objective of this section is to analyse the thermal behaviour of the complexes. The confirmation of the composition of the polymeric structures and the evaluation of the crystal water molecules. The TG/DTA results were investigated in three parts. The first step is described as leaving the coordinated water molecules in the polymeric structures. Interesting results were observed from P¹Ni and P²Co that exothermic degradation of metalated polymers. The exothermic degradation causes the temperature rises than the program rate; therefore, the small peaks were discovered on the TG/DTA curves (Supplementary Figures S11 and S13).^49,50 The decomposition of the aromatic group from the polymers is the second part of the degradation of the polymeric structures depending on the monomeric unit. In the final step, the remaining substances are attributed as metal oxides depending on the metals and monomers.

Luminescence properties

The solid state emission and excitation studies of the polymers (P¹ and P²) and their metalated versions were investigated. The obtained data are given in Figure 2.

Figure 2.

Emission and excitation spectra of the ligands and complexes.

The photoluminescence properties of the ligands and their complexes were investigated in a solid state because of the insolubility of the polymers and the metalated polymers (Supplementary Table S1). The polymeric structure and its metal complexes have higher fluorescent intensive peaks. If they were compared with the previous studies, it could be explained by the polymeric structures consisting of a high number of the repeated units, such as benzene, the imine groups as a linker. The photoluminescent behaviours of the polymeric structures results from the benzene ring, the imine groups, π-π*, the ligand metal charge transfer (LMCT) and the metal ligand charge transfer (MLCT), respectively. Furthermore, the metalated polymeric structures in particular have multiple unpredictable inter-/intra-molecular interaction, which gives a unique rigidity, and the special crinkly shape of the polymers can be clearly seen in the FESEM images (Figures 3 and 4).⁵¹ Inter-/intra-molecular interactions and the induced-strain polymeric structure restricts the ability of the C–C bond rotation and the decreased regulated benzene π-π stacking on the polymeric structure. Therefore, the radiationless vibrational relaxation channels clearly reduce, and the fluorescent intensity of the polymers slightly increases without quenching.^37,52,53 Additionally, even the polymeric structure rigidity and the emission wavelength of the metalated polymers show a very small red shift towards the 5–6 nm lower energies. The photoluminescent properties of P¹ and P² and their metalated complexes have mostly overlapped excited and emission peaks that are located very intensively at approximately 290–300 nm and 590–615 nm, respectively. The main peaks seen at 300 nm are attributed to an intra-ligand transition π-π* backbone of the polymers, and the others appearing at around 600 nm are assigned to the mixture of the intra-ligand transition, the ligand metal charge transfer (LMCT) and the metal ligand charge transfer (MLCT).^54–57 If one of the interesting spectrums, which belongs to the P²-Co_em complexes, is compared with P², it reveals that they overlapped and shifted peaks at the 302 and 307 nm regions. These data also matche the FT-IR results (Table 2) of the imine group, where the metalated polymers have a lower frequency than the backbone of the polymers. It is especially seen that the imine peak exhibits a 56 cm⁻¹ red shift from the P² to P²-Co complex. This red shift is associated with the ligand metal charge transfer (LMCT) from the imine nitrogen to the metal d orbitals.^48,57

Figure 3.

Field emission scanning electron microscopy images of P¹ and their complexes.

Figure 4.

Field emission scanning electron microscopy images of P2 and their complexes.

The morphological analysis

The surface morphological structures of the compounds were inspected with FESEM.

The perspective descriptions of the polymeric ligands, P¹ and P², have an almost well-uniformed spherical shape, while the average size of P¹(a) is nearly 230 nm and 420 nm for P²(b), according to the size distribution results. It is clearly seen with the FESEM pictures that both the orientation of the polymeric structure slightly decreased to smaller sizes and diverse shapes after the metal complexes (Figures 3 and 4). Clearly, the polymeric complexes are also differentiated from each other depending on the transition metal, such as P²-Ni being a much smaller particle size of 21.6 nm. The P²-Cu is similar to the worm shape with a 120 nm length and 23.4 nm thickness. However, the P²-Co is almost 100 nm average sizes with the spherical shape. On the other hand, even though P¹ and P² are also spherical, the shape of the P¹ metal complexes slightly differs from P¹ and P². In addition to the difference between P¹ and P², each of the metal complexes has variety of the shape and size. For example, P¹-Co has a spherical shape with a 200 nm size and P¹-Cu is mostly angular shaped with an 18 nm size; however, P¹-Ni has round plate shape with the 20 nm average size. In comparing the P¹ complexes with the P², one of the biggest distinctions can be interestingly discovered between the shape of P¹-Cu, which is like a worm, and P²-Cu, which is angular. Thus, the FESEM results demonstrated that the polymers exhibit different shapes and sizes after the metalation processes.

Electrical conductivity

The FPP electrical conductivity values of the polymeric compounds were measured via the four-probe technique from the sample pellets, which designed 1 mm thick and 1.0 cm in diameter under a hydraulic pressure of 10 tons. The electrical conductivity test was calculated undoped with iodine during the experimental parts.

The XRD (Supplementary Figures S15 and S16), the FESEM and the BET results showed that the coordination of the nitrogen atom to the metals changed the direction of the monomeric unit in the polymer. Furthermore, according to the FT-IR data complexation of the polymer breaks of the π-π stacking on the polymer chain, which is seen as a red shift after the metalation, the electrical conductivity (Table 3) slightly decimated after the metalation processes.^57–63 The electrical conductivity is carried out through intra-molecular and inter-molecular interactions.⁶⁴ Conversely to P¹, P² has higher electrical conductivity, which could be illustrated by the intermolecular resonance through the polymeric structure. The resonance structures of the para position electrons are permitted to the delocalisation along with the polymeric structures, while the double-bond electrons on the meta position in the benzene ring are disallowed for the delocalisation on the polymer.^51,65,66 Therefore, the delocalisation of the electrons on the polymeric structures improves the conductivity.⁵ The intra-molecular forces, the π-π stacking and the hydrogen bonding of the nitrogen atoms on the imine group also contribute to the higher conductivity for the P² para position.^{14,63,64,67–69} Moreover, the very dark colour of the polymer and the metalated complexes correspond to the extended π system, and the polymers have higher conductivity than the monomeric structures.^60,70 The transition metals, which are π-d-conjugated coordination polymers, increase the conductivity. The diminishment of conductivity can be depending on the low coordination numbers.^{5,12,14–16,40,71} According to the experimental results, the amount of metal is lower than the theoretical calculation, which can be because the metals have a low coordination number on the polymeric structure.^72–74 The ICP, FT-IR and the conductivity results match perfectly because the number of the donated electrons change depending on the valance electron configuration of Co(d⁷), Ni(d⁸) and Cu(d⁹). The decrescent of the conductivity from Co(d⁷) and Ni(d⁸) to Cu(d⁹), respectively, is meaningful, which agrees with the electronic configuration of the transition metals. In a consequence of electronic configuration, the Co has higher electron deficiency if it is compared with the Ni and Cu; hence, the Co-metalated polymers perform the lowest conductivity. In addition to the previous data, the XRD pattern of the polymers and the metalated polymers were investigated (Supplementary Figures S15 and S16). The results demonstrated that new diffraction peaks appear after the metalation of the polymers, depending on the increasing crystallinity. However, the contribution of crystallinity on conductivity is still uncertain for our current XRD results, so it is not discussed in here.

Table 3.

Electrical conductivity and surface area results of the compounds.

Sample	Conductivity (S/cm)	BET Surface Area (m²/g)
P ¹	1.06x10⁻⁴	2.2593
P¹-Co	6.5x10⁻⁶	4.8402
P¹-Ni	6.6x10⁻⁶	0.9227
P¹-Cu	6.8x10⁻⁶	2.9936
P ²	1.5x10⁻¹	0.8163
P²-Co	2.2x10⁻⁵	1.8763
P²-Ni	6.6x10⁻⁵	2.6536
P²-Cu	7.3x10⁻⁵	1.0529

Conclusions

The insoluble and high-temperature melting point polymer that is more than 300^°C and its metalated complexes were successfully synthesised. According to the FESEM data, the coordination bonds during the metalation processes have revealed modification on the morphology of the polymers, shape and size. Similar to the FESEM and FT-IR data, the electrical conductivity of the polymer clearly diminished after metalation. The electrical conductivity showed a remarkable decrease because the new coordination bond breaks the π-π stacking and the delocalisation electrons on the polymeric structure. A similar effect is also shown for the surface area data increases after the metalation processes. Additionally, the data and all the other results also support and demonstrate that the coordination bond during the metalation processes causes a new morphological structure of the polymer; therefore, all of the properties changed slightly after the metalation processes.

Supplemental Material

sj-pdf-1-ppc-10.1177_09673911211048287 – Supplemental Material for The effect of metalation processes on polymer morphology and conductivity properties

Supplemental Material, sj-pdf-1-ppc-10.1177_09673911211048287 for The effect of metalation processes on polymer morphology and conductivity properties by Oğuz Yunus Sarıbıyık, İlyas Gönül, Burak Ay and Serkan Karaca in Polymers and Polymer Composites

Footnotes

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding

The author(s) received no financial support for the research, authorship, and/or publication of this article.

ORCID iD

Oğuz Yunus Sarıbıyık

Supplementary material

Supplementary Material for this article is available online.

References

BaşAkar

OMA

Serin

Özcanli

, et al. Variation of spark plug type and spark gap with hydrogen and methanol added gasoline fuel: performance characteristics. Int J Hydrogen Energ 2020; 45: 26513–26521. DOI: 10.1016/j.ijhydene.2020.03.110

Gozmen Sanli

Ozcanli

Serin

. Assessment of thermodynamic performance of an IC engine using microalgae biodiesel at various ambient temperatures. FUEL 2020; 277: 118108. DOI: 10.1016/j.fuel.2020.118108

SanliUludamar

BGE

Ozcanli

. Evaluation of energetic-exergetic and sustainability parameters of biodiesel fuels produced from palm oil and opium poppy oil as alternative fuels in diesel engines. FUEL 2019; 258: 116116. DOI: 10.1016/j.fuel.2019.116116

Xie

. Electrochemical performance of transition metal-coordinated polypyrrole: a mini review. Chem Rec 2019; 19: 2370–2384. DOI: 10.1002/tcr.201800192

Yuan Chen

, et al. A one-dimensional π-d conjugated coordination polymer for sodium storage with catalytic activity in negishi coupling. Angew Chem Int Edition 2019; 58: 14731–14739. DOI: 10.1002/anie.201908274

Yibing Xie

. Electrochemical cycling stability of nickel (II) coordinated polyaniline. Synth Met 2018; 237: 29–39. DOI: 10.1016/j.synthmet.2018.01.011

Jiang

, et al. Multifunctional covalent organic frameworks for high capacity and dendrite-free lithium metal batteries. Energ Storage Mater 2020; 25: 334–341. DOI: 10.1016/j.ensm.2019.10.005

Kevin

Wood

Neil

, et al. Lithium metal anodes: toward an improved understanding of coupled morphological, electrochemical, and mechanical behavior. ACS Energ Lett 2017; 2: 664–672. DOI: 10.1021/acsenergylett.6b00650

Yakui Mu

. Theoretical and experimental comparison of electrical properties of nickel (II) coordinated and protonated polyaniline. J Phys Chem C 2019; 123: 18232–18239. DOI: 10.1021/acs.jpcc.9b04550.

10.

Seung-Hyeok Kim

HHL

Kim

J-M

You

, et al. Heteromat-framed metal-organic coordination polymer anodes for high-performance lithium-ion batteries. Energ Storage Mater 2019; 19: 130–136. DOI: 10.1016/j.ensm.2019.02.010

11.

Xiaojie Yin

Sun

L-P

, et al. Revealing the effect of cobalt-doping on Ni/Mn-based coordination polymers towards boosted Li-Storage performances. Energ Storage Mater 2020; 25: 846–857. DOI: 10.1016/j.ensm.2019.09.005

12.

Xing Huang

Cui

Wei

, et al. Conductive copper benzenehexathiol coordination polymer as hydrogen evolution catalyst. ACS Appl Mater Inter 2017; 9: 40752–40759. DOI: 10.1021/acsami.7b14523

13.

Xing Huang

Liu

Lei

, et al. Superconductivity in a Copper(II)-based coordination polymer with perfect kagome structure. Angew Chem Int Ed 2018; 57: 146–150. DOI: 10.1002/anie.201707568

14.

Wang

Hou

Chen

, et al. Atwo-dimensional metal–organic polymer enabled by robust nickel–nitrogen and hydrogen bonds for exceptional sodium-ion storage. Angew Chem Int Ed 2020; 59: 22126–22131. DOI: 10.1002/anie.202008726

15.

Roman

Lukas

Roch

, et al. Facile synthesis of potassium tetrathiooxalate the “true” monomer for the preparation of electron-conductive poly(nickelethylenetetrathiolate). Tetrahedron 2017; 73: 2250–2254. DOI: 10.1016/j.tet.2017.03.010

16.

AkankshaMenon

KRMWW

Kommandur

Yee

SK.

. Progress in nickel-coordinated polymers as intrinsically conducting n-type thermoelectric materials. Adv Electron Mater 2019; 5: 1800884. DOI: 10.1002/aelm.201800884

17.

Ana Katherine Díaz-Duran

Viva

. N-doped mesoporous carbons cobalt derived from coordination polymer as supercapacitors. Electrochimica Acta 2019; 299: 987–998. DOI: 10.1016/j.electacta.2019.01.023

18.

J-J

Wang

C-C

Guo

, et al. Two zigzag chain-like lanthanide(III) coordination polymers based on the rigid 1,3-adamantanedicarboxylic acid ligand: Crystal structure, luminescence and magnetic properties. Polyhedron 2017; 126: 17–22. DOI: 10.1016/j.poly.2017.01.010

19.

Davarcı

Zorlu

. Group 12 metal coordination polymers built on a flexible hexakis(3-pyridyloxy)cyclotriphosphazene ligand: effect of the central metal ions on the construction of coordination polymers. polyhedron 2017; 127: 1–8. DOI: 10.1016/j.poly.2017.01.040

20.

Beheshtia

Nozariana

Babadi

, et al. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies. J Solid State Chem 2017; 249: 70–79. DOI: 10.1016/j.jssc.2016.12.013

21.

D-X

Wang

C-C

Wang

, et al. Two novel 2D coordination polymers constructed from 5aminoisophthalic acid and 4,40-bipyridyl ligands: Syntheses, crystal structure, and photocatalytic performance. J Mol Struct 2017; 1135: 129–137. DOI: 10.1016/j.molstruc.2017.01.051

22.

Shuai-Liang Yang

Y-YY

Ren

Zhang

C-X

, et al. High proton conductivity in a nickel(ii) complex and its hybrid membrane. Dalton Trans 2019; 6: 2190–2196. DOI: 10.1039/C8DT04171G

23.

Szafranowska

Beck

. 5-Cyanotetrazolate as a ligand and linker in copper(II) complexes and coordination polymers. Eur J Inorg Chem 2013; 2013: 3167–3177. DOI: 10.1002/ejic.201201483

24.

Krautwurst

Smets

Lamann

, et al. How does the fluorination of the linker affect the stability of trimesate-based coordination polymers and metal−organic frameworks?. Inorg Chem 2019; 58: 8622–8632. DOI: 10.1021/acs.inorgchem.9b00940

25.

Heinke

Wöll

. Surface-mounted metal–organic frameworks: crystalline and porous molecular assemblies for fundamental insights and advanced applications. Adv Mater 2019; 31: 1806324. DOI: 10.1002/adma.201806324

26.

Desai

Sharma

Let

, et al. N-donor linker based metal-organic frameworks (MOFs): Advancement and prospects as functional materials. Coord Chem Rev 2019; 395: 146–192. DOI: 10.1016/j.ccr.2019.05.020

27.

Baul

TSB

Kehie

Duthie

, et al. Dinuclear organotin(IV) coordination polymers derived from Schiff bases with L-aspartic acid. J Organomet Chem 2017; 838: 24–26. DOI: 10.1016/j.jorganchem.2017.03.016

28.

Song

Zhang

Chen

, et al. Pure-supramolecular-linker approach to highly connected metal− organic frameworks for CO₂ Capture. J Am Chem Soc 2019; 141: 14539–14543. DOI: 10.1021/jacs.9b07422

29.

Hoque

Almeida

Cattralla

, et al. Effect of cross-linking on the performance of polymer inclusion membranes (PIMs) for the extraction, transport and separation of Zn(II). J Membr Sci 2019; 589: 117256. DOI: 10.1016/j.memsci.2019.117256

30.

Mehraa

Lia

Yang

, et al. Engineering molecular interaction in polymeric hybrids: effect of thermal linker and polymer chain structure on thermal conduction. Composites B 2019; 166: 509–515. DOI: 10.1016/j.compositesb.2019.02.029

31.

Yanga

Huang

Gogoll

, et al. Effect of the linker in terephthalate-functionalized conducting redox polymers. Electrochimica Acta 2016; 222: 149–155. DOI: 10.1016/j.electacta.2016.10.183

32.

Sezer

Yeşilel

Şahin

, et al. Zinc(II) and cadmium(II) coordination polymers containing phenylenediacetate and bis(imidazol-1-ylmethyl)benzene linkers: the effect of ligand isomers on the solid state structures. J Solid State Chem 2017; 252: 8–21. DOI: 10.1016/j.jssc.2017.04.038

33.

Es-haghi

Bouhendi

Marandi

, et al. An investigation into novel multifunctional cross-linkers effect on microgel prepared by precipitation polymerization. Reactive Funct Polym 2013; 73: 524–530. DOI: 10.1016/j.reactfunctpolym.2012.11.006

34.

Cruz

Silva

Souza

PPD

, et al. Cross-linking effect on thermal, conducting and electrochemical properties of an elastomeric polymer electrolyte. Solid State Ionics 2003;159: 301–311. DOI: 10.1016/S0167-2738(03)00034-1

35.

Çanakçı

Serin

. Synthesis of new azo dye polymers based on naphthol by oxidative polycondensation: antimicrobial activity and fastness studies. J Polym Res 2020; 27: 1. DOI: 10.1007/s10965-019-1982-3

36.

Gönül

Karaca

, et al. Novel copper(II) complexes of two tridentate ONN type ligands: synthesis, characterization, electrical conductivity and luminescence properties. Inorg Chim Acta 2018; 477: 75–83. DOI: 10.1016/j.ica.2018.02.026

37.

Yanga

Zhang

Zhu

, et al. Difunctional chemosensor for Cu(2) and Zn (2) based on Schiff base modified anthryl derivative with aggregation-induced emission enhancement and piezochromic characteristics. J Mater Chem C 2014; 3: 1994–2002. DOI: 10.1039/C4TC02616K

38.

El-Nahrawya ABAH

Khattabb

Ahmed

, et al. Development of electrically conductive nanocomposites from cellulose nanowhiskers, polypyrrole and silver nanoparticles assisted with Nickel(III) oxide nanoparticles. Reactive Funct Polym 2020; 149: 104533. DOI: 10.1016/j.reactfunctpolym.2020.104533

39.

Marco Amores

Sakaushi

Nishihara

. Reversible energy storage in layered copper-based coordination polymers: unveiling the influence of the ligand’s functional group on their electrochemical properties. J Phys Chem C 2020; 124: 9215–9224. DOI: 10.1021/acs.jpcc.0c01486

40.

Kapaev

RRISZ

Kurmaev

Keith

, et al. A nickel coordination polymer derived from 1,2,4,5-tetraaminobenzene for fast and stable potassium battery anodes. Chem Comm 2020; 56: 1541–1544. DOI: 10.1039/C9CC07748K

41.

Roman Kapaev

RSO

Zhidkov

Kurmaev

, et al. Nickel(II) and copper(II) coordination polymers derived from 1,2,4,5-tetraaminobenzene for lithium-ion batteries. Chem Mater 2019; 31: 5197–5205. DOI: 10.1021/acs.chemmater.9b01366

42.

Gonül

Karaca

, et al. Synthesis, characterization, electrical conductivity and luminescence properties of two copper(II) complexes with tridentate N₂O chelating ligands containing imine bond. J Mol Struct 2018; 1156: 465–472. DOI: 10.1016/j.molstruc.2017.12.020

43.

Gönül

Fakı

, et al. Cobalt(II), nickel(II) and copper(II) complexes of a Schiff base ligand: synthesis, structural characterization and luminescence properties. Transit Metal Chem 2018; 43: 73–81. DOI: 10.1007/s11243-017-0195-z

44.

Gönül

Karaca

, et al. Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction. Designed Monomers Polym 2017; 20: 441–448. DOI: 10.1080/15685551.2017.1332139

45.

Avşar

Gökbulut

, et al. A novel catalyst system for the synthesis of N,N′Methylenebisacrylamide from acrylamide. Designed Monomers and Polmers 2017; 20: 434–440. DOI: 10.1080/15685551.2017.1332138

46.

Gonul

Kose

Ceyhan

, et al. Methoxy group containing bidentate Schiff base ligands and their transition metal complexes: Synthesis, structural characterisation, photoluminescence, antioxidant capacity and superoxide dismutase activity studies. Inorg Chim Acta 2016; 453: 522–530. DOI: 10.1016/j.ica.2016.09.004

47.

Durak

Delikanlı

Kani

, et al. Crystal structure of an unsymmetrical Schiff base, immobilization of its cobalt and manganese complexes on a silica support, and catalytic studies. Transit Met Chem 2013; 38: 199–206. DOI: 10.1007/s11243-012-9678-0

48.

Rahman

LHA

Abu‐Dief

El‐Khatib

, et al. Sonochemical synthesis, structural inspection and semiconductor behavior of three new nano sized Cu(II), Co(II) and Ni(II) chelates based on tri‐dentate NOO imine ligand as precursors for metal oxides. Appl Organometal Chem 2018; 32: 1–12. DOI: 10.1002/aoc.4174

49.

Stanislav Dubinsky

GSG

Shte

Silverstein

. Thermal degradation of poly(acrylic acid) containing copper nitrate. Polym Degrad Stab 2004; 86.

50.

Yih-Shing Duh

T-CH

Chen

J-R

Kao

C-S

. Study on exothermic oxidation of acrylonitrile-butadiene-styrene (ABS) resin powder with application to ABS processing safety. Polym MDPI 2010; 2: 174–187. DOI: 10.3390/polym2030174

51.

Wang

Zheng

, et al. Schiff base particles with aggregation-induced enhanced emission: random aggregation preventing π–π stacking. J Mater Chem C 2013; 1: 6952–6959. DOI: 10.1039/C3TC31626B

52.

Gusev

Shulgin

Braga

, et al. Synthesis and photophysical properties of Zn(II) Schiff base complexes possessing strong solvent-dependent solid-state fluorescence. polyhedron 2018; 155: 202–208. DOI: 10.1016/j.poly.2018.08.019

53.

Bhattacharjee

Datta

Das

, et al. Novel photoluminescent mesogenic Schiff-base ligands bearing [N₄O₄] donors and their bimetallic Zn(II) complexes. Mater Sci Eng C 2012; 32: 735–741. DOI: 10.1016/j.msec.2012.01.016

54.

Majumdar

Dey

Das

, et al. Heterometallic Zn(II)-K(I) complex with salen-type Schiff-base ligand: Synthesis, crystal structure, solid-state photoluminescent property and theoretical study. J Mol Struct 2019; 1185: 112e120. DOI: 10.1016/j.molstruc.2019.02.092

55.

Liu

Schanze

. Photophysics of π-conjugated oligomers and polymers that contain transition metal complexes. J Photochem Photobiol C: Photochem Rev 2002; 3: 1–23. DOI: 10.1016/S1389-5567(02)00004-7

56.

Zhang

Wang

. Crystal structures and photoluminescent properties of two d10 metal coordination polymers based on 5-aminodiacetic isophthalic acid. Inorg Chem Commun 2014; 45: 75–78. DOI: 10.1016/j.inoche.2014.04.009

57.

Zhang

Wong

W-Y

. Energy materials based on metal Schiff base complexes. Coord Chem Rev 2018; 355: 180–198. DOI: 10.1016/j.ccr.2017.08.007

58.

Jiang

Zhang

, et al. Exploring the interfacial phase and π–π stacking in aligned carbon nanotube/polyimide nanocomposites. Nanomaterial 2020; 10: 1–12. DOI: doi:10.3390/nano10061158

59.

Wang

Zhou

, et al. Molecular engineered conjugated polymer with high thermal conductivity. Sci Adv 2018; 4: 1–6. DOI: 10.1126/sciadv.aar3031

60.

Wang

W-J

Hao

Chen

C-Y

, et al. Red-shift in fluorescence emission of D–A type asymmetrical Zn(II) complexes by extending the p– p stacking interaction. RSC Adv 2017; 7: 20488–20493. DOI: 10.1039/c7ra01135k

61.

AhmedEL-Mahdy

Laia

M-Y

Kuo

S-W

. A highly fluorescent covalent organic framework as a hydrogen chloride sensor: roles of Schiff base bonding and π-stacking. J Mater Chem C 2020; 8: 9520–9528. DOI: 10.1039/D0TC01872D

62.

Dong

Y-B

Smith

Loye

H-Cz

. New inorganic/organic coordination polymers generated from bidentate schiff-base ligands. Inorg Chem 2000; 39: 4927–4935. DOI: 10.1021/ic0006504

63.

Ze-Hua

Chun-Ying

Ji-Hui

, et al. Structural dependence of π-π interactions in dithiocarbazato and thiosemicarbazato nickel complexes. New J Chem 2000; 12: 1057–1062. DOI: 10.1039/b004846l

64.

Gönül

. Synthesis and structural characterization of ONO type tridentate ligands and their Co(II) and Ni(II) complexes: Investigation of electrical conductivity and antioxidant properties. Inorg Chim Acta 2019; 495: 119027. DOI: 10.1016/j.ica.2019.119027

65.

Dineshkumar

Muthusamy

. Synthesis and spectral characterization of cross linked rigid structured schiff base polymers: effect of substituent position changes on optical, electrical, and thermal properties. Polymer-Plastics Tech Eng 2016; 55: 368–378. DOI: 10.1080/03602559.2015.1098680

66.

Ceyhan

Köse

Tümer

, et al. Structural characterization of some Schiff base compounds: Investigation of their electrochemical, photoluminescence, thermal and anticancer activity properties. J Lumin 2013; 143: 623–634. DOI: 10.1016/j.jlumin.2013.06.002

67.

Rita Leonesa

RCS

José

Esperança

, et al. Effect of storage time on the ionic conductivity of chitosan-solid polymer electrolytes incorporating cyano-based ionic liquids. Electrochimica Acta 2017; 232: 22–29. DOI: 10.1016/j.electacta.2017.02.053

68.

Parameswaran

NNV

Devendran

Nagarajan

, et al. Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application. Physica B: Condensed Matter 2017; 515: 89–98. DOI: 10.1016/j.physb.2017.03.043

69.

Janiak

. A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands. J Chem Soc Dalton Trans 2000; 21: 885–3896. DOI: 10.1039/B003010O

70.

Makode

Yaul

Bhadange

, et al. Physicochemical characterization, thermal, and electrical conductivity studies of some transition metal complexes of bis-chelating schiff base. Russ J Inorg Chem 2009; 54: 1372–1377.

71.

Yuanyuan Ling

Zhou

Tao

, et al. Metal-organosulfide coordination polymer nanosheet array as a battery-type electrode for an asymmetric supercapacitor. Inorg Chem 2020; 59: 7360–7369. DOI: 10.1021/acs.inorgchem.0c00916

72.

Sagar

Vidya

Krishna

, et al. Synthesis, characterization, luminescence and dna binding properties of ln (III)-schiff base family. J Chilean Chem Soc 2017; 62. DOI: 10.4067/S0717-97072017000200006

73.

Ommenya Ean

Andala

Synthesis

. Characterization and antibacterial activity of schiff base, 4-Chloro-2-{(E)-[(4-Fluorophenyl)imino]methyl}phenol Metal (II) Complexes. J Chem 2020; 8: 1–8. DOI: 10.1155/2020/1745236

74.

Taniyuki Furuyama

Saikawa

Maeda

, et al. One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region. Nature 2019; 9: 16528. DOI: 10.1038/s41598-019-53014-7

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