Abstract
Novel tin(IV) halo complexes of an N-confused tetraphenylporphyrin with different axial ligands have been synthesized and characterized by various spectroscopic methods including X-ray crystallographic analysis. The molecular structures of the dichloro and dibromo derivatives possess perfect octahedral geometries, which are nearly comparable to the corresponding regular porphyrin complexes. In contrast, the iodide/triiodide complex obtained by a same reaction manner, demonstrated that the tin(IV) cation is slightly displaced towards axially coordinated iodide anion, giving rise to the different electronic structure due to the tautomeric form of N-confused porphyrin ligand. These structural differences reflected to the distinct photophysical and electrochemical properties. The Sn(IV) complexes are near IR luminescent, however the unsymmetrical axial coordination of iodide and triiodide anions in the tin(IV) N-confused porphyrin complex allows, in particular, the longer emission lifetimes and a smaller singlet-triplet energy gap, which were investigated by steady-state and time-resolved spectroscopies as well as theoretical calculations.
| Original language | English |
|---|---|
| Pages (from-to) | 361-371 |
| Number of pages | 11 |
| Journal | Journal of Porphyrins and Phthalocyanines |
| Volume | 19 |
| Issue number | 1-3 |
| DOIs | |
| Publication status | Published - Jan 1 2015 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
Near-infrared luminescent Sn(IV) complexes of N-confused tetraphenylporphyrin : Effect of axial anion coordination. / Basu, Arghya; Kitamura, Motoki; Mori, Shigeki; Ishida, Masatoshi; Xie, Yongshu; Furuta, Hiroyuki.
In: Journal of Porphyrins and Phthalocyanines, Vol. 19, No. 1-3, 01.01.2015, p. 361-371.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Near-infrared luminescent Sn(IV) complexes of N-confused tetraphenylporphyrin
T2 - Effect of axial anion coordination
AU - Basu, Arghya
AU - Kitamura, Motoki
AU - Mori, Shigeki
AU - Ishida, Masatoshi
AU - Xie, Yongshu
AU - Furuta, Hiroyuki
PY - 2015/1/1
Y1 - 2015/1/1
N2 - Novel tin(IV) halo complexes of an N-confused tetraphenylporphyrin with different axial ligands have been synthesized and characterized by various spectroscopic methods including X-ray crystallographic analysis. The molecular structures of the dichloro and dibromo derivatives possess perfect octahedral geometries, which are nearly comparable to the corresponding regular porphyrin complexes. In contrast, the iodide/triiodide complex obtained by a same reaction manner, demonstrated that the tin(IV) cation is slightly displaced towards axially coordinated iodide anion, giving rise to the different electronic structure due to the tautomeric form of N-confused porphyrin ligand. These structural differences reflected to the distinct photophysical and electrochemical properties. The Sn(IV) complexes are near IR luminescent, however the unsymmetrical axial coordination of iodide and triiodide anions in the tin(IV) N-confused porphyrin complex allows, in particular, the longer emission lifetimes and a smaller singlet-triplet energy gap, which were investigated by steady-state and time-resolved spectroscopies as well as theoretical calculations.
AB - Novel tin(IV) halo complexes of an N-confused tetraphenylporphyrin with different axial ligands have been synthesized and characterized by various spectroscopic methods including X-ray crystallographic analysis. The molecular structures of the dichloro and dibromo derivatives possess perfect octahedral geometries, which are nearly comparable to the corresponding regular porphyrin complexes. In contrast, the iodide/triiodide complex obtained by a same reaction manner, demonstrated that the tin(IV) cation is slightly displaced towards axially coordinated iodide anion, giving rise to the different electronic structure due to the tautomeric form of N-confused porphyrin ligand. These structural differences reflected to the distinct photophysical and electrochemical properties. The Sn(IV) complexes are near IR luminescent, however the unsymmetrical axial coordination of iodide and triiodide anions in the tin(IV) N-confused porphyrin complex allows, in particular, the longer emission lifetimes and a smaller singlet-triplet energy gap, which were investigated by steady-state and time-resolved spectroscopies as well as theoretical calculations.
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UR - http://www.scopus.com/inward/citedby.url?scp=84928566786&partnerID=8YFLogxK
U2 - 10.1142/S1088424615500212
DO - 10.1142/S1088424615500212
M3 - Article
AN - SCOPUS:84928566786
VL - 19
SP - 361
EP - 371
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
SN - 1088-4246
IS - 1-3
ER -