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An insight into the molecular structures, theoretical calculation and catalytic activities of novel heterotrinuclear [CuCe] and heterohexanuclear [CuY] bis(salamo)-based complexes
Two heteropolynuclear complexes, namely [Cu 2 (L)Ce(NO 3 ) 3 ] and [{Cu 2 (L)Y(NO 3 ) 2 (μ-AcO)}{Cu 2 (L)Y(NO 3 ) 2 (μ-NO 3 )(CH 3 OH)}]·4CH 3 OH, were synthesized through the reaction of a newly synthesized bis(salamo)-based ligand (H 4 L), Cu(OAc) 2 ·H 2 O and Ln(NO 3 ) 3 ·6H 2 O (Ln = Ce and Y),...
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| Published in: | New journal of chemistry 2020-12, Vol.44 (45), p.19836-19849 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Two heteropolynuclear complexes, namely [Cu
2
(L)Ce(NO
3
)
3
] and [{Cu
2
(L)Y(NO
3
)
2
(μ-AcO)}{Cu
2
(L)Y(NO
3
)
2
(μ-NO
3
)(CH
3
OH)}]·4CH
3
OH, were synthesized through the reaction of a newly synthesized bis(salamo)-based ligand (H
4
L), Cu(OAc)
2
·H
2
O and Ln(NO
3
)
3
·6H
2
O (Ln = Ce and Y), respectively. Single crystal structure analyses showed that the [Cu
II
2
Ce
III
] and [Cu
II
4
Y
III
2
] complexes contained similar trinuclear [Cu
II
2
Ln
III
] structures. The difference was that the [Cu
II
4
Y
III
2
] complex consisted of two crystallographically independent and chemically different trinuclear complexes with coordination and free solvent molecules. Among the two heteropolynuclear metal complexes, only the [Cu
II
2
Ce
III
] complex showed catecholase activity and benzoxazinone synthase activity under normal temperature and aerobic conditions. For catecholase activity, the calculated
K
cat
of the [Cu
II
2
Ce
III
] complex was 346.5 h
−1
, and the
K
cat
of p-benzoxazinone synthase activity was 9.73 h
−1
. Compared with the [Cu
II
4
Y
III
2
] complex, we speculated that the main reason for the high catalytic function of the [Cu
II
2
Ce
III
] complex is the presence of three nitrate groups coordinated with the central Ce
III
atom. Evidence from mass spectrometry and cyclic voltammetry curves indicated that there may be heterometallic cooperation, in which Ce
III
binds to the substrate, while the metallic copper transformed between Cu
II
and Cu
I
through redox reactions. In addition, the catalytic mechanism was inferred through electrospray mass spectrometry and cyclic voltammetry, and fluorescence properties were studied and Hirshfeld surface analyses were also conducted.
Two heteropolynuclear complexes, [Cu
II
2
Ce
III
] [Cu
2
(L)Ce(NO
3
)
3
] and [{Cu
2
(L)Y(NO
3
)
2
(μ-AcO)}{Cu
2
(L)Y(NO
3
)
2
(μ-NO
3
)(CH
3
OH)}]·4CH
3
OH, were synthesized. It was found that only the [Cu
II
2
Ce
III
] complex showed high catecholase and benzoxazinone synthase like catalytic activity. |
|---|---|
| ISSN: | 1144-0546 1369-9261 |
| DOI: | 10.1039/d0nj04126b |