Designing diverse coordination modes for the covalent attachment of Wells-Dawson type polyoxometalate onto porphyrins

Five covalently bonded polyoxometalate (POM)-porphyrin hybrids were synthesized by reacting the Wells-Dawson type polyoxometalate [N(C 4 H 9 ) 4 ] 5 H 4 P 2 W 15 V 3 O 62 with five tris-functionalized porphyrins containing different numbers of tris groups at different peripheral positions. These hyb...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2023-08, Vol.52 (34), p.1185-11858
Main Authors: Asif, Hafiz Muhammad, Ashfaq, Hafiza Fareeha, Zhou, Yunshan, Zhang, Lijuan, Iqbal, Arshad, Hu, Xin, Shehzad, Farooq Khurum
Format: Article
Language:English
Subjects:
Chemical analysis
Covalence
Electron transfer
Fluorescence
Functional groups
Mass spectrometry
NMR
Nuclear magnetic resonance
Polyoxometallates
Porphyrins
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Summary:Five covalently bonded polyoxometalate (POM)-porphyrin hybrids were synthesized by reacting the Wells-Dawson type polyoxometalate [N(C 4 H 9 ) 4 ] 5 H 4 P 2 W 15 V 3 O 62 with five tris-functionalized porphyrins containing different numbers of tris groups at different peripheral positions. These hybrids were thoroughly characterized using elemental analysis, NMR ( 1 H, 31 P, and 51 V), mass spectrometry (ESI-MS, MALID-TOF-MS), FT-IR, UV-Vis, and fluorescence spectroscopies. The results proved that different quantities (one, two, and three) of the vanadium-capped Wells-Dawson type metal-oxide cluster P 2 W 15 V 3 O 62 9− can be grafted onto a porphyrin moiety via covalent bonding with different orientations, depending on the number and position of peripheral functional groups on the porphyrin. Interestingly, remarkable fluorescence quenching (60% in 3Py-P@1POM, 75% in trans -2PyP@2POM, 80% in cis -2PyP@2POM, 85% in cis -2PhP@2POM, and 55% in 1Py-P@3POM, as compared to the fluorescence intensity of their corresponding porphyrin precursor) was observed under excitation ( λ exc = 328 nm), indicating electron transfer from the porphyrin moiety to the POM moiety through covalent linkage. Five covalently bonded polyoxometalate-porphyrin hybrids were synthesized by reacting the Wells-Dawson type P 2 W 15 V 3 O 62 9− with five tris-functionalized porphyrins containing different numbers of tris groups at different peripheral positions.
ISSN:1477-9226
1477-9234
DOI:10.1039/d3dt01879b