Journal Article

PUBDB-2026-00873

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Navigating the Bio‐Inspired Structure‐Function Landscape: Spectroscopy Driven Finding of Hidden Radical Oxidation in Co‐porphyrinic Porous Organic Polymer

Boro, B. ; Biswas, C. ; Vuong, T. H. ; Nandy, S.Extern*DESY* ; Shrotri, A. ; Tsuji, Y. (Corresponding author) ; Rabeah, J. (Corresponding author) ; Mondal, J. (Corresponding author)Extern*

2026
WILEY-VCH Verlag GmbH & Co. KGaA Weinheim

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Please use a persistent id in citations: doi:10.1002/smtd.202501981

Abstract: The conventional synthesis of acetophenone via the Friedel-Crafts reaction is a highly waste-intensive process. Consequently, thedevelopment of more sustainable and efficient alternatives is important. In this regard, radical oxidation represents a promising,environmentally benign route for acetophenone production. In this work, we designed a cobalt porphyrin-based metalatedporous organic polymer (Co@POR-POP), a highly active catalytic system, offering a potentially viable and cleaner approach toacetophenone production, utilizing styrene as the starting material. The catalyst exhibits a high surface area (BET = 650 m 2 g−1 )with bimodal pores, and delivers more than 90% yield of acetophenone under ambient conditions with excellent selectivity.Synchrotron-based XAFS spectroscopy study revealed a square-planar Co-N 4 coordination environment with coordinationnumber (CN) ≈4 and Co─N bond distance of ∼1.93 Å, with no evidence of Co–Co scattering, confirming the presence of isolatedactive sites. In situ EPR spectroscopy investigation displayed g⊥ = 2.049 and g∥ = 1.985 with hyperfine couplings A⊥ = 49.8 MHzand A∥ = 46.16 MHz, alongside an organic radical signal at g = 2.003. Spin-trapping with DMPO detected both hydrogen (∙H) andstyrene (∙C) radicals, validating a radical-mediated mechanism. DFT calculations established a thermodynamically favourablepathway with an overall energy drop of −4.5 eV, supported by spin density localization at the Co centre and significant d-π orbitaloverlap facilitating O2 activation. Overall, this work presents a new avenue of exploring novel organic transformation reactionsusing metalated porous organic polymer, opening scope for further investigations in this domain.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. PETRA-S (FS-PETRA-S)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)

Experiment(s):

1. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2026

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Database coverage:
; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Wiley ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 10 ; JCR ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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