Journals / Osmaniye Korkut Ata Üniversitesi Fen Bilimleri Enstitüsü Dergisi / 2026 / Cilt: 9 Sayı: 4

Investigation of the Effect of Anderson–Evans type Polyoxometalate Incorporation on the Optoelectronic Properties of Carbazole-Based Polymer Films

Karbazol Bazlı Polimer Filmlerin Optoelektronik Özellikleri Üzerine Anderson–Evans Tipi Polioksometalat Katkısının Etkisinin İncelenmesi

Yasemin Torlak(PAMUKKALE UNIVERSITY)0000-0001-5964-2532
Pages
2448–2473
Publication Date
2026-09-09
🏛️Bibliographic metadata and full text access for this article are provided via DergiPark.
DergiPark Record ↗
✨

AI Summary & Key Takeaways

AI Insight
⚡ TL;DR(Too Long; Didn't Read)

The results demonstrate that incorporating Anderson–Evans type polyoxometalate clusters into carbazole-based conducting polymers is an effective strategy to develop advanced electrochromic materials with improved stability and optoelectronic performance.

📌 3 Key Takeaways

🎯
Objective & Hypothesis:Composite materials based on polyoxometalates (POMs) have attracted increasing attention due to their excellent proton and electron transport properties, high thermal stability, structural diversity, and tunable redox characteristics.
📊
Key Findings & Data:Recently, the integration of POM clusters with conducting polymers has emerged as an effective strategy to improve electrochemical and optoelectronic performances of functional materials.
💡
Conclusion & Impact:The results demonstrate that incorporating Anderson–Evans type polyoxometalate clusters into carbazole-based conducting polymers is an effective strategy to develop advanced electrochromic materials with improved stability and optoelectronic performance.
🔬Design:Araştırma Makalesi
📍Scope:Comprehensive Sample
⚙️Variables:Polioksometalatlar · AlW6-POM · Karbazol bazlı iletken polimerler

Abstract

Composite materials based on polyoxometalates (POMs) have attracted increasing attention due to their excellent proton and electron transport properties, high thermal stability, structural diversity, and tunable redox characteristics. Recently, the integration of POM clusters with conducting polymers has emerged as an effective strategy to improve electrochemical and optoelectronic performances of functional materials. In this study, an organic–inorganic hybrid nanocomposite film consisting of a carbazole-based conducting polymer (pCz9T) and a Anderson-Evans type polyoxometalate, [Ph₄P]₃[Al(OH)₆W₆O₁₈] (AlW6-POM), was successfully fabricated via electrochemical polymerization on an ITO electrode. The electrochemical and spectroelectrochemical properties of the pristine polymer film and the AlW6-POM/pCz9T composite film were systematically investigated using cyclic voltammetry and UV–Vis spectroelectrochemistry. The incorporation of AlW6-POM clusters into the polymer matrix resulted in significant improvements in the electrochemical and optical performance of the film. The electrochemical stability increased from 74% to 90% after repeated cycling, while the optical contrast (ΔT) increased from 27% to 64%, indicating enhanced electrochromic performance. Furthermore, the charge density increased from 0.7052 to 1.644 mC cm⁻², and the switching time decreased from 1.5 s to 1.0 s, demonstrating faster electrochromic response. In addition, the coloration efficiency improved from 139.1 to 235.3 cm² C⁻¹, confirming the improved charge storage and optical modulation capability of the composite film. These improvements can be attributed to the synergistic interaction between the redox-active AlW6-POM clusters and the conjugated polymer backbone, which facilitates electron transfer and enhances electrochemical activity. The results demonstrate that incorporating Anderson–Evans type polyoxometalate clusters into carbazole-based conducting polymers is an effective strategy to develop advanced electrochromic materials with improved stability and optoelectronic performance.

Özet

Polioksometalat (POM) temelli kompozit malzemeler, üstün proton ve elektron taşınım özellikleri, yüksek termal kararlılıkları, yapısal çeşitlilikleri ve ayarlanabilir redoks özellikleri nedeniyle son yıllarda giderek artan bir ilgi görmektedir. Son zamanlarda, POM kümelerinin iletken polimerlerle birleştirilmesi, fonksiyonel malzemelerin elektrokimyasal ve optoelektronik performanslarını geliştirmek için etkili bir yaklaşım olarak öne çıkmıştır. Bu çalışmada, karbazol bazlı iletken polimer (pCz9T) ile Dawson tipi polioksometalat olan lityum içeren [Ph₄P]₃[Al(OH)₆W₆O₁₈] (AlW6-POM) bileşiğinden oluşan organik-inorganik hibrit nanokompozit film, ITO elektrot yüzeyinde elektrokimyasal polimerizasyon yöntemi ile başarıyla hazırlanmıştır. Saf polimer film ile AlW6-POM/pCz9T kompozit filmin elektrokimyasal ve spektroelektrokimyasal özellikleri döngüsel voltametri ve UV–Vis spektroelektrokimya teknikleri kullanılarak sistematik olarak incelenmiştir. AlW6-POM kümelerinin polimer matrisi içerisine dahil edilmesi, filmin elektrokimyasal ve optik performansında önemli iyileşmelere yol açmıştır. Tekrarlı döngüler sonrasında elektrokimyasal stabilite %74’ten %90’a yükselirken, optik kontrast (ΔT) değeri %27’den %64’e artarak elektrokromik performansın belirgin şekilde geliştiğini göstermiştir. Ayrıca, yük yoğunluğu 0.7052 mC cm⁻²’den 1.644 mC cm⁻²’ye yükselmiş ve anahtarlama süresi 1.5 s’den 1.0 s’ye düşerek daha hızlı elektrokromik tepki elde edilmiştir. Bunun yanında, renklenme verimliliği 139.1 cm² C⁻¹’den 235.3 cm² C⁻¹’ye artarak kompozit filmin yük depolama ve optik modülasyon kapasitesinin iyileştiğini doğrulamıştır. Elde edilen bu iyileşmeler, redoks aktif AlW6-POM kümeleri ile konjuge polimer omurgası arasındaki sinerjik etkileşime bağlanabilir. Bu etkileşim elektron transferini kolaylaştırmakta ve sistemin elektrokimyasal aktivitesini artırmaktadır. Sonuç olarak, Anderson–Evans tipi polioksometalat kümelerinin karbazol bazlı iletken polimer yapısına entegre edilmesinin, gelişmiş stabilite ve optoelektronik performansa sahip ileri elektrokromik malzemelerin geliştirilmesi için etkili bir strateji olduğu gösterilmiştir.

🔖

Cite This Article

Torlak, Y. (2026). Investigation of the Effect of Anderson–Evans type Polyoxometalate Incorporation on the Optoelectronic Properties of Carbazole-Based Polymer Films. Osmaniye Korkut Ata Üniversitesi Fen Bilimleri Enstitüsü Dergisi, Cilt: 9 Sayı: 4, 2448–2473. https://doi.org/10.47495/okufbed.1904611

📄 Full Text PDF Viewer

📄

PDF görüntüleyici hazırlanıyor...

References (58)

  1. Al-Eggiely H., Alguail AA., Gvozdenović MM., Jugović BZ., Grgur BN. Zinc polypyrrole-air sea water battery. International Journal of Electrochemical Science 2016; 11(12): 10270–10277.
  2. Al-Yasari A., Van Steerteghem N., Kearns H., El Moll H., Faulds K., Wright JA., Brunschwig BS., Clays K., Fielden J. Organoimido-polyoxometalate nonlinear optical chromophores: A structural, spectroscopic, and computational study. Inorganic Chemistry 2017; 56(17): 10181–10194.
  3. Ammam M. Polyoxometalates: Formation, structures, principal properties, main deposition methods and application in sensing. Journal of Materials Chemistry A 2013; 1(21): 6291–6312.
  4. Anjass M., Lowe GA., Streb C. Molecular vanadium oxides for energy conversion and energy storage: current trends and emerging opportunities. Angewandte Chemie - International Edition 2021; 60(14): 7522–7532.
  5. Anyushin AV., Kondinski A., Parac-Vogt TN. Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications. Chemical Society Reviews 2020; 49(2): 382–432.
  6. Avciozbek H. Synthesis and characterization of Anderson–Evans type polyoxometalates, antibacterial properties. Turkish Journal of Chemistry 2023; 47(4): 742–748.
  7. Blasco-Ahicart M., Soriano-López J., Galán-Mascarós JR. Conducting organic polymer electrodes with embedded polyoxometalate catalysts for water splitting. ChemElectroChem 2017; 4(12): 3296–3301.
  8. Buru CT., Farha OK. Strategies for incorporating catalytically active polyoxometalates in metal–organic frameworks for organic transformations. Chemical Reviews 2020; 120(5): 5345–5360.
  9. Carraro M., Gross S. Hybrid materials based on the embedding of organically modified transition metal oxoclusters or polyoxometalates into polymers for functional applications: A review. Materials 2014; 7(5): 3956–3989.
  10. Chen S., Xiang Y., Banks MK., Peng C., Xu W., Wu R. Polyoxometalate-coupled MXene nanohybrid via poly(ionic liquid) linkers and its electrode for enhanced supercapacitive performance. Nanoscale 2018; 10(42): 20043–20052.
  11. Dieterle M., Weinberg G., Mestl G. Raman spectroscopy of molybdenum oxides – part I: structural characterization of oxygen defects in MoO3−x by DR UV/Vis, Raman spectroscopy and X-ray diffraction. Physical Chemistry Chemical Physics 2002; 4(5): 812–821.
  12. Dikmen G. Investigation of tautomeric structures of 6-aza-2-thiouracil-5-carboxylic acid using vibrational spectroscopy along with DFT theoretical method. Eskişehir Technical University Journal of Science and Technology A 2021; 22(1): 23–35.
  13. Dubal DP., Lee SH., Kim JG., Kim WB., Lokhande CD. Porous polypyrrole clusters prepared by electropolymerization for a high performance supercapacitor. Journal of Materials Chemistry 2012; 22(7): 3044–3052.
  14. George JM., Antony A., Mathew B. Metal oxide nanoparticles in electrochemical sensing and biosensing: a review. Microchimica Acta 2018; 185(7): 358.
  15. Guimard NK., Gomez N., Schmidt CE. Conducting polymers in biomedical engineering. Progress in Polymer Science 2007; 32(8–9): 876–921.
  16. Guzel M., Torlak Y., Choi H., Ak M. Designed hybrid organic–inorganic nanocomposite film based on synergistic effect of conducting polymer and Keggin-type polyoxometalate clusters. Materials Research Bulletin 2023; 167: 112406.
  17. Guzel M., Torlak Y., Choi H., Ak M. “Perfect match” of the carbazole-based conducting polymer and polyoxometalate nanocomposite components for enhanced optical and electrical properties. European Polymer Journal 2023; 186: 111857.
  18. Guzel M., Torlak Y., Karatas E., Ak M. Optical and electrical properties of monolacunary Keggin-type polyoxometalate/star-shaped polycarbazole nanocomposite film. Journal of The Electrochemical Society 2019; 166(8): 313–319.
  19. Haciismailoglu M. Effects of the PPy layer thickness on Co–PPy composite films. Applied Surface Science 2015; 356: 817–826.
  20. Herrmann S., Ritchie C., Streb C. Polyoxometalate–conductive polymer composites for energy conversion, energy storage and nanostructured sensors. Dalton Transactions 2015; 44(16): 7092–7104.
  21. Ji Y., Huang L., Hu J., Streb C., Song YF. Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage and sensor systems. Energy & Environmental Science 2015; 8(3): 776–789.
  22. Karabay B., Pekel LC., Cihaner A. A pure blue to highly transmissive electrochromic polymer based on poly(3,4-propylenedioxyselenophene) with a high optical contrast ratio. Macromolecules 2015; 48(5): 1352–1357.
  23. Karakas H., Ak M. N-heterocyclic carbene containing benzothiazol-2-ylidene-Ru(II) and Pd(II) complexes functionalized with butyl-linked carbazole moiety: synthesis, characterization and electropolymerization. European Polymer Journal 2022; 181: 111630.
  24. Kato C., Nishihara S., Tsunashima R., Tatewaki Y., Okada S., Ren XM., Inoue K., Long DL., Cronin L. Quick and selective synthesis of Li6[α-P2W18O62]·28H2O soluble in various organic solvents. Dalton Transactions 2013; 42(32): 11363-11370.
  25. Kruse JH., Langer M., Romanenko I., Trentin I., Hernández-Castillo D., González L., Schacher FH., Streb C. Polyoxometalate-soft matter composite materials: design strategies, applications, and future directions. Advanced Functional Materials 2022; 32(51): 2208428.
  26. Li W., Song B., Manthiram A. High-voltage positive electrode materials for lithium-ion batteries. Chemical Society Reviews 2017; 46(10): 3006–3059.
  27. Liu S., Kurth DG., Möhwald H., Volkmer D. A thin-film electrochromic device based on a polyoxometalate cluster. Advanced Materials 2002; 14(3): 225–228.
  28. Long DL., Burkholder E., Cronin L. Polyoxometalate clusters, nanostructures and materials: from self-assembly to designer materials and devices. Chemical Society Reviews 2007; 36(1): 105–121.
  29. Long DL., Tsunashima R., Cronin L. Polyoxometalates: building blocks for functional nanoscale systems. Angewandte Chemie - International Edition 2010; 49(10): 1736–1758.
  30. Marcano S., Lentink S., Moussawi MA., Parac-Vogt TN. Solution dynamics of hybrid Anderson–Evans polyoxometalates. Inorganic Chemistry 2021; 60(14): 10215–10226.
  31. Naseer R., Ali B., Laffir F., Kailas L., Dickinson C., Armstrong G., McCormac T. Transition metal-substituted Krebs-type polyoxometalate-doped PEDOT films. Langmuir 2019; 35(34): 11007–11015.
  32. Okujima T., Matsumoto H., Mori S., Nakae T., Takase M., Uno H. Synthesis of cyclo[8]pyrrole–polyoxometalate double-decker complex. Tetrahedron Letters 2016; 57(29): 3160–3162.
  33. Otero TF., Cheng SA., Alonso D., Huerta F. Hybrid materials polypyrrole/PW12O40³⁻: physical, spectroscopic and electrochemical characterization. Journal of Physical Chemistry B 2000; 104(45): 10528–10533.
  34. Passadis S., Kabanos TA., Song YF., Miras HN. Self-assembly in polyoxometalate and metal coordination-based systems: synthetic approaches and developments. Inorganics 2018; 6(3): 71.
  35. Proust A., Matt B., Villanneau R., Guillemot G., Gouzerh P., Izzet G. Functionalization and post-functionalization: a step towards polyoxometalate-based materials. Chemical Society Reviews 2012; 41(22): 7605–7622.
  36. Ravanbakhsh H., Dianat S., Hosseinian A. Fabrication of a polyoxotungstate/metal–organic framework/phosphorus-doped reduced graphene oxide nanohybrid modified glassy carbon electrode. RSC Advances 2022; 12(15): 9210–9222.
  37. Selvam J., Samannan B., Peter P., Thavasikani J. Synthesis, characterization, and solution studies of polyoxometalate-doped conducting polymers. Polymers and Polymer Composites 2021; 29(5): 373–382.
  38. Setiadi A., Fujii H., Kasai S., Yamashita KI., Ogawa T., Ikuta T., Kanai Y., Matsumoto K., Kuwahara Y., Akai-Kasaya M. Room-temperature discrete-charge-fluctuation dynamics of a single molecule adsorbed on a carbon nanotube. Nanoscale 2021; 13(30): 10674–10683.
  39. Soganci T., Gumusay O., Soyleyici HC., Ak M. Synthesis of highly branched conducting polymer architecture for electrochromic applications. Polymer 2018; 134: 187–195.
  40. Soganci T., Torlak Y., Ak M., Ersoz M. Poly(dithienylpyrrole)/Keggin-type hybrid material: enhanced optical and electrical properties of conjugated polymers via polyoxometalates. Synthetic Metals 2018; 244: 54–60.
  41. Stuckart M., Monakhov KY. Polyoxometalates as components of supramolecular assemblies. Chemical Science 2019; 10(16): 4364–4376.
  42. Suárez-Guevara J., Ruiz V., Gómez-Romero P. Stable graphene–polyoxometalate nanomaterials for application in hybrid supercapacitors. Physical Chemistry Chemical Physics 2014; 16(38): 20411–20414.
  43. Sumliner JM., Lv H., Fielden J., Geletii YV., Hill CL. Polyoxometalate multi-electron-transfer catalytic systems for water splitting. European Journal of Inorganic Chemistry 2014; 2014(4): 635–644.
  44. Suppes GM., Cameron CG., Freund MS. A polypyrrole/phosphomolybdic acid–poly(3,4-ethylenedioxythiophene)/phosphotungstic acid asymmetric supercapacitor. Journal of The Electrochemical Society 2010; 157(9): A1030.
  45. Swenson L., Khan MI. Electrochemical properties of polyoxometalate composite materials containing multiple redox centers. Chemical Papers 2019; 73: 2611–2617.
  46. Tsuboi M., Hibino M., Mizuno N., Uchida S. Crystalline polyoxometalate (POM)–polyethylene glycol (PEG) composites aimed as non-humidified intermediate-temperature proton conductors. Journal of Solid State Chemistry 2016; 234: 9–14.
  47. Ueda T. Electrochemistry of polyoxometalates: from fundamental aspects to applications. ChemElectroChem 2018; 5(6): 823–838.
  48. Wang DG., Liang Z., Gao S., Qu C., Zou R. Metal–organic framework-based materials for hybrid supercapacitor application. Coordination Chemistry Reviews 2020; 404: 213093.
  49. Wang X., Liu J., Pope MT. New polyoxometalate/starch nanomaterial: synthesis, characterization and antitumoral activity. Dalton Transactions 2003; 5: 957–960.
  50. Wang Y., Liu Q., Zhang H. Polypyrrole-based POM hybrid films with enhanced electrochemical performance. Synthetic Metals 2020; 79: 6929.
  51. Wu P., Wang Y., Huang B., Wang Y. Anderson-type polyoxometalates: From structures to functions. Nanoscale 2021; 13: 7119–7133.
  52. Xu Z., Wang M., Fan W., Zhao J., Wang H. The synthesis of new donor–acceptor polymers and electrochemical properties. Electrochimica Acta 2015; 160: 271–280.
  53. Xue CM., Li SX., Zhang L., Sha JQ., Zheng TY., Zhang QN., Li L. Hydrothermal synthesis, characterization and electrocatalytic/photocatalytic activities of new polyoxometalate-based hybrid compound. Journal of Inorganic and Organometallic Polymers and Materials 2013; 23(6): 1468–1476.
  54. Zamolo VA., Modugno G., Lubian E., Cazzolaro A., Mancin F., Giotta L., Mastrogiacomo D., Valli L., Saccani A., Krol S., Bonchio M., Carraro M. Selective targeting of proteins by hybrid polyoxometalates: interaction between a bis-biotinylated hybrid conjugate and avidin. Frontiers in Chemistry 2018; 6: 1–10.
  55. Zarnegaryan A. Facile synthesis of polyoxometalate supported on magnetic graphene oxide as a hybrid catalyst for efficient oxidation of aldehydes. Scientific Reports 2022; 12(1): 18491–18498.
  56. Zhang GF., Wang R., Yu FL., Zhao HX. Clean fuel-oriented investigation of thiophene oxidation by hydrogen peroxide using polyoxometalate as catalyst. Chemical Papers 2009; 63(5): 617–619.
  57. Zhang S., Liu R., Li S., Dolbecq A., Mialane P., Suo L., Bi L., Zhang B., Liu T., Wu C., Yan L., Su Z., Zhang G., Keita B. Simple and efficient polyoxomolybdate-mediated synthesis of novel graphene and metal nanohybrids for versatile applications. Journal of Colloid and Interface Science 2018; 514: 507–516.
  58. Zhang L., Wang X., Li Y. Electrochromic properties of PEDOT/POM composite films. Journal of Materials Chemistry C 2020; 8: 100036.