TY - JOUR
T1 - Hybrid Zn-β-Aminoporphyrin–Carbon Nanotubes
T2 - Pyrrolidine and Direct Covalent Linkage Recognition, and Multiple-Photo Response
AU - Rebelo, Susana L. H.
AU - Laia, César A. T.
AU - Szefczyk, Monika
AU - Guedes, Alexandra
AU - Silva, Ana M. G.
AU - Freire, Cristina
N1 - info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/DL 57%2F2016/DL57%2F2016%2FCP1334%2FCP1644%2FCT0001/PT#
The work was supported through projects UIDB/50006/2020 and UIDP/50006/2020, funded by FCT/MCTES, through national funds. S.L.H.R. (Refs. REQUIMTE/EEC2018/30) and A.M.G.S. thank FCT (Fundação para a Ciência e Tecnologia) for funding through program DL 57/2016—Norma transitória.
PY - 2023/11/5
Y1 - 2023/11/5
N2 - To unveil and shape the molecular connectivity in (metallo)porphyrin–carbon nanotube hybrids are of main relevance for the multiple medicinal, photoelectronic, catalytic, and photocatalytic applications of these materials. Multi-walled carbon nanotubes (MWCNTs) were modified through 1,3-dipolar cycloaddition reactions with azomethine ylides generated in situ and carrying pentafluorophenyl groups, followed by immobilization of the β-amino-tetraphenylporphyrinate Zn(II). The functionalities were confirmed via XPS and FTIR, whereas Raman spectroscopy showed disruptions on the graphitic carbon nanotube surface upon both steps. The functionalization extension, measured via TGA mass loss and corroborated via XPS, was 0.2 mmol·g−1. Photophysical studies attest to the presence of the different porphyrin–carbon nanotube connectivity in the nanohybrid. Significantly different emission spectra and fluorescence anisotropy of 0.15–0.3 were observed upon variation of excitation wavelength. Vis-NIR absorption and flash photolysis experiments showed energy/charge transfer in the photoactivated nanohybrid. Moreover, evidence was found for direct reaction of amino groups with a carbon nanotube surface in the presence of molecular dipoles such as the zwitterionic sarcosine amino acid.
AB - To unveil and shape the molecular connectivity in (metallo)porphyrin–carbon nanotube hybrids are of main relevance for the multiple medicinal, photoelectronic, catalytic, and photocatalytic applications of these materials. Multi-walled carbon nanotubes (MWCNTs) were modified through 1,3-dipolar cycloaddition reactions with azomethine ylides generated in situ and carrying pentafluorophenyl groups, followed by immobilization of the β-amino-tetraphenylporphyrinate Zn(II). The functionalities were confirmed via XPS and FTIR, whereas Raman spectroscopy showed disruptions on the graphitic carbon nanotube surface upon both steps. The functionalization extension, measured via TGA mass loss and corroborated via XPS, was 0.2 mmol·g−1. Photophysical studies attest to the presence of the different porphyrin–carbon nanotube connectivity in the nanohybrid. Significantly different emission spectra and fluorescence anisotropy of 0.15–0.3 were observed upon variation of excitation wavelength. Vis-NIR absorption and flash photolysis experiments showed energy/charge transfer in the photoactivated nanohybrid. Moreover, evidence was found for direct reaction of amino groups with a carbon nanotube surface in the presence of molecular dipoles such as the zwitterionic sarcosine amino acid.
KW - 1,3-dipolar cycloadditions
KW - carbon nanotube hybrids
KW - covalent linkage
KW - photo-responsive materials
KW - zinc(II) porphyrin
UR - http://www.scopus.com/inward/record.url?scp=85176473315&partnerID=8YFLogxK
U2 - 10.3390/molecules28217438
DO - 10.3390/molecules28217438
M3 - Article
C2 - 37959857
AN - SCOPUS:85176473315
SN - 1420-3049
VL - 28
JO - Molecules
JF - Molecules
IS - 21
M1 - 7438
ER -