Exploiting Boron Coordination: B←N Bond Supports a [2+2] Photodimerization in the Solid State and Generation of a Diboron Bis‐Tweezer for Benzene/Thiophene Separation

Campillo‐Alvarado, Gonzalo; D'mello, Kyle P.; Swenson, Dale C.; Mariappan, S. V. Santhana; Höpfl, Herbert; Morales‐Rojas, Hugo; MacGillivray, Leonard R.

doi:10.1002/anie.201812174

Cited by 63 publications

(34 citation statements)

References 39 publications

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“…Interestingly, guest recognition may occur in both cavities within this framework resembling a double‐tweezer host, and structural syn / anti ‐isomerism is feasible, which might enable the encapsulation of even two different guest molecules (Scheme c). Moreover, these double‐tweezer hosts were shown to perform “catch‐release” cycles of polycyclic aromatic hydrocarbons (PAHs) such as pyrene from solution mixtures, to accomplish the separation of o ‐xylene from an equimolar mixture of o ‐, m ‐ and p ‐xylene isomers by enrichment through fractional crystallization, and to behave as molecular scavengers for the selective removal of sulfur‐based aromatics such as thiophene …”

Section: Introductionmentioning

confidence: 99%

Boron–Nitrogen Double Tweezers Comprising Arylboronic Esters and Diamines: Self‐Assembly in Solution and Adaptability as Hosts for Aromatic Guests in the Solid State

2020

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The thermodynamic stability of 1 : 1 and 2 : 1 boron–nitrogen (B←N) adducts formed between aromatic boronic esters with mono‐ and diamines was studied in solution by NMR and UV‐vis spectroscopy with association energies (ΔG°) ranging from −11 to −28 kJ mol−1. The effect of different substituents in the boronic ester, the nature of the diamine linker, and the effect of the solvent was explored. Stable 2 : 1 B←N adducts with diamines such as 1,3‐diaminopropane were produced in solutions of hydrogen‐bonding acceptor solvents (acetonitrile and ethyl acetate), which can be isolated in the solid state as crystalline solvates, whereas the use of noncoordinating solvents such as 1,2‐dichloroethane afforded mainly 1 : 1 B←N adducts. In suitable combinations, aromatic bis‐pyridyl diamines produced stable 2 : 1 B←N adducts that were isolated either as solvent‐free solids, solvates, or cocrystals. In these crystalline forms, double‐tweezer hosts were observed with an exceptional syn/anti conformational guest‐adaptability driven by simultaneous donor‐acceptor and C−H⋅⋅⋅π interactions in the tweezer cavities, resembling preorganized covalent tweezer hosts. Interestingly, cocrystals with electron‐rich guests such as tetrathiafulvalene and pyrene showed non‐centrosymmetric crystal lattices with infinite π‐stacked donor–acceptor columns.

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Section: Introductionmentioning

confidence: 99%

Boron–Nitrogen Double Tweezers Comprising Arylboronic Esters and Diamines: Self‐Assembly in Solution and Adaptability as Hosts for Aromatic Guests in the Solid State

2020

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“…10 g , h Recently, the B←N dative bond has appeared to serve as a good alternative to traditional non-covalent and metal–coordinate bonds, to build supramolecular network/host–guest-based crystalline assemblies, for various applications. 11–20 In general, the donation of electrons from the N-donor ligand to the electron-deficient boron atom (empty p-orbital) stabilizes such type of bonding. It has also been observed that the electronic properties of the interacting partner strongly influence the strength of the B←N dative bond.…”

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Effect of chemical substitution on the construction of boroxine-based supramolecular crystalline polymers featuring B←N dative bonds

2022

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“…Stacking of the C=C bonds in the dimer fulfilled the geometric criteria of Schmidt for a [2+2]-photocycloaddition affording rctt-1,3-bis(4′-pyridyl)-2,4-bis(phenyl)cyclobutane (ppcb) upon UV irradiation (Scheme 6). 32 Crystallization of the components afforded a T-shaped boronic ester adduct of composition (be)•(4-sbz) wherein 4-sbz was positioned orthogonally to be. Self-assembly of two monoboron adducts generated a discrete dimer with a head-to-tail geometry (ht) sustained by ••• and C-H••• contacts (Figure 6a,b).…”

Section: Boronic Esters As Templates For [2+2]-photocycloadditions In the Solid Statementioning

confidence: 99%

Opportunities Using Boron to Direct Reactivity in the Organic Solid State

Campillo‐Alvarado

MacGillivray

2020

Synlett

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This Account describes work by our research group that highlights opportunities to utilize organoboron molecules to direct chemical reactivity in the organic solid state. Specifically, we convey a previously unexplored use of hydrogen bonding of boronic acids and boron coordination in boronic esters to achieve [2+2]-photocycloadditions in crystalline solids. Organoboron molecules act as templates or ‘shepherds’ to organize alkenes in a suitable geometry to undergo regio- and stereoselective [2+2]-photocycloadditions in quantitative yields. We also provide a selection of publications that served as an inspiration for our strategies and offer challenges and opportunities for future developments of boron in the field of materials and solid-state chemistry.1 Introduction1.1 Template Strategy for [2+2]-Photocycloadditions in the Solid State2 Boronic Acids as Templates for [2+2]-Photocycloadditions in the Solid State2.1 Supramolecular Catalysis of [2+2]-Photocycloadditions in the Solid State Using Boronic Acids3 Boronic Esters as Templates for [2+2]-Photocycloadditions in the Solid State3.1 Application of Photoproducts: Separation of Thiophene from Benzene through Crystallization3.2 Crystal Reactivity of B←N-Bonded Adducts: The Case of Styrylthiophenes4 Conclusions and Perspectives

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Exploiting Boron Coordination: B←N Bond Supports a [2+2] Photodimerization in the Solid State and Generation of a Diboron Bis‐Tweezer for Benzene/Thiophene Separation

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 63 publications

References 39 publications

Boron–Nitrogen Double Tweezers Comprising Arylboronic Esters and Diamines: Self‐Assembly in Solution and Adaptability as Hosts for Aromatic Guests in the Solid State

Boron–Nitrogen Double Tweezers Comprising Arylboronic Esters and Diamines: Self‐Assembly in Solution and Adaptability as Hosts for Aromatic Guests in the Solid State

Effect of chemical substitution on the construction of boroxine-based supramolecular crystalline polymers featuring B←N dative bonds

Opportunities Using Boron to Direct Reactivity in the Organic Solid State

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