Self-complementary Structure of Bisporphyrin Dimer

Hisano, Naoyuki; Hirao, Takehiro; Haino, Takeharu

doi:10.1246/cl.210393

Cited by 9 publications

(4 citation statements)

References 35 publications

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“…During the course of studies on the development of host molecules, bisporphyrin cleft 1 possessing two porphyrin molecules connected with pyridine-2,6-dicarboxamide was reported as a handy cleft-shaped molecular tweezer (Figure ). , The cleft-shaped cavity of 1 is maintained by the assistance of the intramolecular hydrogen bonding between the basic nitrogen and the amide NHs. Electron-deficient aromatic guest molecules are encapsulated within the electron-rich cleft-shaped cavity in a ratio of 1:1 through intermolecular charge transfer interactions.…”

Section: Introductionmentioning

confidence: 99%

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Hisano

Haino

2022

J. Org. Chem.

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The host–guest complexation of a bisporphyrin cleft with various electron-deficient guest molecules was studied in solution and in the solid-state. X-ray crystal structures of a bisporphyrin cleft with naphthalene dianhydride and 2,4,7-trinitrofluorenone reveal that these guest molecules were located within the bisporphyrin cleft and formed ideal π–π stacking interactions in a host–guest ratio of 1:1. Isothermal titration calorimetry determined the binding constants and thermodynamic parameters for the 1:1 host–guest complexations in 1,2-dichloroethane and toluene. Two types of enthalpy–entropy compensation effects were found: (1) The tightly stacked host–guest structures restrict guest movement within the cleft, which results in significant desolvation with large intrinsic entropies. (2) The loosely bound guests maintain their molecular freedom within the bisporphyrin cleft, which leads to less desolvation with small intrinsic entropies. Chiral guest encapsulation directed the clockwise and anticlockwise twisted conformations of the bisporphyrin units, which induced bisignate CDs.

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Section: Introductionmentioning

confidence: 99%

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Hisano

Haino

2022

J. Org. Chem.

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“…It is known that a bisporphyrin unit is self‐assembled to form its complementary dimer [16c,20] . We previously reported that the self‐assembly of a tetrakisporphyrin monomer afforded supramolecular polymers, which generated unresolved, broad proton signals due to aggregation [17c] .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and cooperative guest binding of tetrameric porphyrin macrocycle

Tanabe,

Hisano,

Haino

2024

ChemistrySelect

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A new family of macrocyclic host molecules that possess two bisporphyrin clefts was synthesized. The tetrameric porphyrin macrocycle provides the two guest binding sites in which two electron‐deficient aromatic molecules are encapsulated through donor‐acceptor and π‐π stacking interactions. The tetrameric porphyrin macrocycle showed positive cooperativity, whereas the nonmacrocyclic analog did not. The preorganization concept drives positive cooperativity, which is directed by the entropy benefit to macrocyclization.

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“…It is known that a bisporphyrin with the pyridine dicarboxamide linkage can be assembled to form its complementary dimer. [15] Thus, 1 was self-assembled in a lipophilic solvent. 1 showed broad and unresolved proton signals even below 1 mmol L À 1 in [D]chloroform (Figure S5); this implied that 1 formed aggregates in solution.…”

Section: Resultsmentioning

confidence: 99%

“…It is known that a bisporphyrin with the pyridine dicarboxamide linkage can be assembled to form its complementary dimer [15] . Thus, 1 was self‐assembled in a lipophilic solvent.…”

Section: Resultsmentioning

confidence: 99%

Negative Homotropic Cooperativity in Guest Binding of a Trisporphyrin Double Cleft

Hisano

Kodama

Haino

2023

Chemistry A European J

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The negative homotropic allostery of a triple‐layered trisporphyrin cleft with two guest binding sites is confirmed. The X‐ray crystal structures of the 1 : 2 host‐guest complexes showed that the trisporphyrin accommodated two guest molecules within the cleft through π–π stacking and donor‐acceptor interactions. In solution, 1H NMR and Job plots showed 1 : 2 host‐guest complexes. Isothermal titration calorimetry (ITC) and UV/vis absorption spectroscopy were employed to evaluate the binding constants and cooperativities. The guest binding of the trisporphyrin showed negative cooperativity and non‐cooperativity depending on the structures of the guest molecules. The correlations between the interaction parameters (α) and Hill constants were determined. ITC experiments showed that the host‐guest complexation of trisporphyrin with electron‐deficient guests incurred an enthalpy penalty in the successive guest binding process. DFT calculations revealed that binding of the first guest reduced the electron density of the central porphyrin plane, which led to an energetic penalty that weakened the successive binding process.

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Self-complementary Structure of Bisporphyrin Dimer

Cited by 9 publications

References 35 publications

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient Aromatic Guests

Synthesis and cooperative guest binding of tetrameric porphyrin macrocycle

Negative Homotropic Cooperativity in Guest Binding of a Trisporphyrin Double Cleft

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