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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.
Supplementary materials
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Supporting Information
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All the synthetic details, spectroscopic data and associated information.
Additional experimental data has been added and minor errors corrected
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S2. Synthesis of photoswitchable ligand 1
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S2. Synthesis of photoswitchable ligand 1
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S3. Photoswitching properties of ligand 1
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S3. Photoswitching properties of ligand 1
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S4. Synthesis of palladium(II) complexes
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S4. Synthesis of palladium(II) complexes
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S5. Preliminary guest binding studies between [Pd2L4](BArF)4 in DCM
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S5. Preliminary guest binding studies between [Pd2L4](BArF)4 in DCM
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S6. Synthesis and characterization of homoleptic cage [Pd2(E-1)4]4+
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S6. Synthesis and characterization of homoleptic cage [Pd2(E-1)4]4+
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S7. Photoswitching of [Pd2(E-1)4]4+
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S7. Photoswitching of [Pd2(E-1)4]4+
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S8. Synthesis and characterization of ligand 2
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S8. Synthesis and characterization of ligand 2
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S9. Synthesis and characterization of homoleptic species [Pd4(2)8]8+ and [Pd3(2)6]6+
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S9. Synthesis and characterization of homoleptic species [Pd4(2)8]8+ and [Pd3(2)6]6+
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S10. Synthesis and characterization of heteroleptic cage [Pd2(E-1)2(2)2]4+
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S10. Synthesis and characterization of heteroleptic cage [Pd2(E-1)2(2)2]4+
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S11. Photoswitching of [Pd2(E-1)2(2)2](BF4)4
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S11. Photoswitching of [Pd2(E-1)2(2)2](BF4)4
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S12. Spartan models of [Pd2(E-1)4]4+, [Pd2(E-1)2(2)2]4+ and [Pd(Z-1)2]2+
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S12. Spartan models of [Pd2(E-1)4]4+, [Pd2(E-1)2(2)2]4+ and [Pd(Z-1)2]2+
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S13. Diffusion NMR data for [Pd2(E-1)4](BF4)4, [Pd4(2)8](BF4)8 and [Pd2(E-1)2(2)2](BF4)4 in DMSO-d6
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S13. Diffusion NMR data for [Pd2(E-1)4](BF4)4, [Pd4(2)8](BF4)8 and [Pd2(E-1)2(2)2](BF4)4 in DMSO-d6
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S14. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM MeNO2 (9:1)
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S14. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM MeNO2 (9:1)
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S15. The effect of solvent on self-assembly
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S15. The effect of solvent on self-assembly
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S16. The effect of 3-chloropyridine (Py) on the self-assembly of [Pd2(E-1)2(2)2](BArF)4 in DCM MeCN (10 :1)
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S16. The effect of 3-chloropyridine (Py) on the self-assembly of [Pd2(E-1)2(2)2](BArF)4 in DCM MeCN (10 :1)
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S17. Guest binding studies in heteroleptic cage [Pd2(E-1)2(2)2](BArF)4 in 11:1 DCM MeCN
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S17. Guest binding studies in heteroleptic cage [Pd2(E-1)2(2)2](BArF)4 in 11:1 DCM : MeCN
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S18. Catalysing the Michael addition between methyl vinyl ketone and benzoyl nitromethane
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S18. Catalysing the Michael addition between methyl vinyl ketone and benzoyl nitromethane
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S19. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM:MeCN (11:1)
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S19. Controlling catalysis with light using [Pd2(E-1)2(2)2](BArF)4 in DCM:MeCN (11:1)
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