Photoswitchable catalysis by a self-assembled molecular cage

12 April 2024, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

A heteroleptic [Pd2L2L'2]4+ coordination cage containing a photoswitchable azobenzene-derived ligand catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane within its cavity. The correspond-ing homoleptic cages are catalytically inactive. The heteroleptic cage can be reversibly disassembled and reassembled using 530 nm light and 405 nm light, respectively, allowing catalysis within the cage to be switched ON and OFF at will.

Keywords

Self-assembly
Coordination Cage
Photoswitch
Photochromism
Catalysis

Supplementary materials

Title
Description
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Title
S2. Synthesis of photoswitchable ligand 1
Description
S2. Synthesis of photoswitchable ligand 1
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Title
S3. Photoswitching properties of ligand 1
Description
S3. Photoswitching properties of ligand 1
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Title
S4. Synthesis of palladium(II) complexes
Description
S4. Synthesis of palladium(II) complexes
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Title
S5. Preliminary guest binding studies between [Pd2L4](BArF)4 in DCM
Description
S5. Preliminary guest binding studies between [Pd2L4](BArF)4 in DCM
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Title
S6. Synthesis and characterization of homoleptic cage [Pd2(E-1)4]4+
Description
S6. Synthesis and characterization of homoleptic cage [Pd2(E-1)4]4+
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Title
S7. Photoswitching of [Pd2(E-1)4]4+
Description
S7. Photoswitching of [Pd2(E-1)4]4+
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Title
S8. Synthesis and characterization of ligand 2
Description
S8. Synthesis and characterization of ligand 2
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Title
S9. Synthesis and characterization of homoleptic species [Pd4(2)8]8+ and [Pd3(2)6]6+
Description
S9. Synthesis and characterization of homoleptic species [Pd4(2)8]8+ and [Pd3(2)6]6+
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Title
S10. Synthesis and characterization of heteroleptic cage [Pd2(E-1)2(2)2]4+
Description
S10. Synthesis and characterization of heteroleptic cage [Pd2(E-1)2(2)2]4+
Actions
Title
S11. Photoswitching of [Pd2(E-1)2(2)2](BF4)4
Description
S11. Photoswitching of [Pd2(E-1)2(2)2](BF4)4
Actions
Title
S12. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCMMeNO2 (9 1)
Description
S12. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCMMeNO2 (9 1)
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Title
S13. The effect of solvent on self-assembly
Description
S13. The effect of solvent on self-assembly
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Title
S14. The effect of 3-chloropyridine (Py) on the self-assembly of [Pd2(E-1)2(2)2](BArF)4 in DCMMeCN (101)
Description
S14. The effect of 3-chloropyridine (Py) on the self-assembly of [Pd2(E-1)2(2)2](BArF)4 in DCMMeCN (101)
Actions
Title
S15. Catalysing the Michael addition between methyl vinyl ketone and benzoyl nitromethane
Description
S15. Catalysing the Michael addition between methyl vinyl ketone and benzoyl nitromethane
Actions
Title
S16. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM:MeCN (11:1)
Description
S16. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM:MeCN (11:1)
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Title
Supporting Information
Description
All the synthetic details, spectroscopic data and associated information.
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