Visible-Light-Mediated Polymerization of 1,3-Benzoxazines with Titanium Metal-Organic Frameworks

Abdollah Omrani; Kerem Kaya; Zeynep Deliballi; Baris Kiskan

doi:10.1021/acsapm.5c01446

Visible-Light-Mediated Polymerization of 1,3-Benzoxazines with Titanium Metal-Organic Frameworks

Abdollah Omrani^*
, Kerem Kaya
, Zeynep Deliballi
, Baris Kiskan^*

^*Corresponding author for this work

Department of Chemistry

Istanbul Technical University
Mazandaran University

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

Titanium-based metal-organic frameworks (MOFs) (MIL-125 based) were utilized as photocatalysts for the first time, in the successful visible-light-mediated polymerization of monofunctional 1,3-benzoxazines (Bzs). Gel permeation chromatography (GPC) analysis revealed that the resulting model polybenzoxazines (PBzs) exhibited relatively high number-average molecular weights (M_n). The photopolymerization process was traced by NMR spectroscopy, evidencing complete monomer conversion with MIL-125 (Ti). Control experiments using UV light or diphenyliodonium hexafluorophosphate demonstrated negligible or no Bz polymerization under the same experimental conditions. To enhance the photocatalytic performance, MIL-125 (Ti) was modified through amine functionalization and silver (Ag) doping, which improved visible-light absorption, as confirmed by UV-vis spectroscopy. Moreover, a mechanism for the photocatalytic polymerization of Bzs was also proposed for which the unique contribution of MIL-125 (Ti) to commence the charge-transfer reaction was highlighted as well.

Original language	English
Pages (from-to)	8280-8289
Number of pages	10
Journal	ACS Applied Polymer Materials
Volume	7
Issue number	12
DOIs	https://doi.org/10.1021/acsapm.5c01446
Publication status	Published - 27 Jun 2025

Bibliographical note

Publisher Copyright:
© 2025 American Chemical Society.

Keywords

MIL-125 (Ti)
benzoxazines
metal−organic frameworks
photocatalyst
polybenzoxazine
visible-light polymerization

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10.1021/acsapm.5c01446

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title = "Visible-Light-Mediated Polymerization of 1,3-Benzoxazines with Titanium Metal-Organic Frameworks",

abstract = "Titanium-based metal-organic frameworks (MOFs) (MIL-125 based) were utilized as photocatalysts for the first time, in the successful visible-light-mediated polymerization of monofunctional 1,3-benzoxazines (Bzs). Gel permeation chromatography (GPC) analysis revealed that the resulting model polybenzoxazines (PBzs) exhibited relatively high number-average molecular weights (Mn). The photopolymerization process was traced by NMR spectroscopy, evidencing complete monomer conversion with MIL-125 (Ti). Control experiments using UV light or diphenyliodonium hexafluorophosphate demonstrated negligible or no Bz polymerization under the same experimental conditions. To enhance the photocatalytic performance, MIL-125 (Ti) was modified through amine functionalization and silver (Ag) doping, which improved visible-light absorption, as confirmed by UV-vis spectroscopy. Moreover, a mechanism for the photocatalytic polymerization of Bzs was also proposed for which the unique contribution of MIL-125 (Ti) to commence the charge-transfer reaction was highlighted as well.",

keywords = "MIL-125 (Ti), benzoxazines, metal−organic frameworks, photocatalyst, polybenzoxazine, visible-light polymerization",

author = "Abdollah Omrani and Kerem Kaya and Zeynep Deliballi and Baris Kiskan",

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doi = "10.1021/acsapm.5c01446",

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T1 - Visible-Light-Mediated Polymerization of 1,3-Benzoxazines with Titanium Metal-Organic Frameworks

AU - Omrani, Abdollah

AU - Kaya, Kerem

AU - Deliballi, Zeynep

AU - Kiskan, Baris

PY - 2025/6/27

Y1 - 2025/6/27

N2 - Titanium-based metal-organic frameworks (MOFs) (MIL-125 based) were utilized as photocatalysts for the first time, in the successful visible-light-mediated polymerization of monofunctional 1,3-benzoxazines (Bzs). Gel permeation chromatography (GPC) analysis revealed that the resulting model polybenzoxazines (PBzs) exhibited relatively high number-average molecular weights (Mn). The photopolymerization process was traced by NMR spectroscopy, evidencing complete monomer conversion with MIL-125 (Ti). Control experiments using UV light or diphenyliodonium hexafluorophosphate demonstrated negligible or no Bz polymerization under the same experimental conditions. To enhance the photocatalytic performance, MIL-125 (Ti) was modified through amine functionalization and silver (Ag) doping, which improved visible-light absorption, as confirmed by UV-vis spectroscopy. Moreover, a mechanism for the photocatalytic polymerization of Bzs was also proposed for which the unique contribution of MIL-125 (Ti) to commence the charge-transfer reaction was highlighted as well.

AB - Titanium-based metal-organic frameworks (MOFs) (MIL-125 based) were utilized as photocatalysts for the first time, in the successful visible-light-mediated polymerization of monofunctional 1,3-benzoxazines (Bzs). Gel permeation chromatography (GPC) analysis revealed that the resulting model polybenzoxazines (PBzs) exhibited relatively high number-average molecular weights (Mn). The photopolymerization process was traced by NMR spectroscopy, evidencing complete monomer conversion with MIL-125 (Ti). Control experiments using UV light or diphenyliodonium hexafluorophosphate demonstrated negligible or no Bz polymerization under the same experimental conditions. To enhance the photocatalytic performance, MIL-125 (Ti) was modified through amine functionalization and silver (Ag) doping, which improved visible-light absorption, as confirmed by UV-vis spectroscopy. Moreover, a mechanism for the photocatalytic polymerization of Bzs was also proposed for which the unique contribution of MIL-125 (Ti) to commence the charge-transfer reaction was highlighted as well.

KW - MIL-125 (Ti)

KW - benzoxazines

KW - metal−organic frameworks

KW - photocatalyst

KW - polybenzoxazine

KW - visible-light polymerization

UR - https://www.scopus.com/pages/publications/105008470588

U2 - 10.1021/acsapm.5c01446

DO - 10.1021/acsapm.5c01446

M3 - Article

AN - SCOPUS:105008470588

SN - 2637-6105

VL - 7

SP - 8280

EP - 8289

JO - ACS Applied Polymer Materials

JF - ACS Applied Polymer Materials

IS - 12

ER -

Visible-Light-Mediated Polymerization of 1,3-Benzoxazines with Titanium Metal-Organic Frameworks

Abstract

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Keywords

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