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Self-assembled via metal-ligand coordination AzaBODIPY-zinc phthalocyanine and AzaBODIPY-zinc naphthalocyanine conjugates: Synthesis, structure, and photoinduced electron transfer

Title
Self-assembled via metal-ligand coordination AzaBODIPY-zinc phthalocyanine and AzaBODIPY-zinc naphthalocyanine conjugates: Synthesis, structure, and photoinduced electron transfer
Authors
Bandi V.El-Khouly M.E.Nesterov V.N.Karr P.A.Fukuzumi S.D'Souza F.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2013
Journal Title
Journal of Physical Chemistry C
ISSN
1932-7447JCR Link
Citation
vol. 117, no. 11, pp. 5638 - 5649
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Using near-IR emitting photosensitizers, viz., zinc phthalocyanine (ZnPc), zinc naphthalocyanine (ZnNc), and BF2-chelated azadipyrromethene (azaBODIPY), donor-acceptor conjugates have been newly formed using the well-known metal-ligand axial coordination approach. To accomplish this task, the electron-deficient azaBODIPY was functionalized to possess either two pyridine or imidazole ligating entities. The X-ray crystal structure of one such derivative revealed the presence of axial binding capable pyridine entities on the azaBODIPY macrocycle. The structural integrity of the newly formed conjugates was established from optical absorption, emission, 1H NMR, electrochemical, and computational methods. The experimentally determined binding constants suggested moderately stable conjugates. The absence of excitation energy transfer from singlet excited azaBODIPY to either ZnPc or ZnNc in the conjugates was confirmed from the steady-state emission measurements. However, free-energy calculations suggested photoinduced electron transfer to be exothermic from singlet excited ZnPc or ZnNc to azaBODIPY. Femtosecond transient studies confirmed such predictions from where occurrence of ultrafast photoinduced electron transfer was observed. The measured rates of charge separation and charge recombination (kCS and kCR) revealed charge stabilization to some extent in these conjugates. © 2013 American Chemical Society.
DOI
10.1021/jp400046b
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자연과학대학 > 화학·나노과학전공 > Journal papers
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