Synthesis and structural characterization of exemplary silyl triptycenes

Mames, Adam; Osior, Agnieszka; Szkudlarek, Piotr Grzegorz; Pietrzak, Mariusz; Szymański, Sławomir; Ratajczyk, Tomasz

doi:10.1039/c9nj00934e

Cited by 2 publications

(7 citation statements)

References 32 publications

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“…As inferred from the 1 H, 29 Si HSQC spectrum (see the supporting information in Ref. 32), the signals at À 38.53 and À 37.86 ppm come from TRPCl-R1 and TRPCl-R2, respectively. In each rotamer, the Si atom is substituted with two carbon atoms, the sp 3 -bridgehead and C Ph atoms.…”

Section: Nmr Measurementsmentioning

confidence: 85%

“…At ambient temperatures, they are long-lived on the NMR time scale. [32] In each rotamer, internal rotations of the phenyl ring about the SiÀ C Ph bond as well as the dynamics of the -OMe group (see Figure S1 in the Supporting Information) remain fast on the NMR time scale even at lowered temperatures, what is evident from the features of the signals in the 1 H NMR spectra concerned. As regards TRPCl-R1, both of the SiÀ H bonds are disposed syn towards the peri-Cl atom and are geometrically equivalent.…”

Section: Introductionmentioning

confidence: 96%

“…In the dichloro derivative, the corresponding values are 217.4 and 190.7 Hz. Strictly analogous diversification of the 1 J(Si,H) values was recently observed in 1,4‐dichlorotriptycene substituted in the sp 3 ‐carbon position with the −SiH 2 PhOMe group (TRPCl) . In solution, TRPCl exists in the form of two interconverting rotamers: TRPCl‐R1 and TRPCl‐R2 differing in the disposition of the −SiH 2 PhOMe group with respect to the peri‐Cl atom.…”

Section: Introductionmentioning

confidence: 99%

“…In solution, TRPCl exists in the form of two interconverting rotamers: TRPCl‐R1 and TRPCl‐R2 differing in the disposition of the −SiH 2 PhOMe group with respect to the peri‐Cl atom. At ambient temperatures, they are long‐lived on the NMR time scale . In each rotamer, internal rotations of the phenyl ring about the Si−C Ph bond as well as the dynamics of the ‐OMe group (see Figure S1 in the Supporting Information) remain fast on the NMR time scale even at lowered temperatures, what is evident from the features of the signals in the 1 H NMR spectra concerned.…”

Section: Introductionmentioning

confidence: 99%

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Blue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density

et al. 2020

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Triptycene derivatives are widely utilized in different fields of chemistry and materials sciences. Their physicochemical properties, often of pivotal importance for the rational design of triptycene‐based functional materials, are influenced by noncovalent interactions between substituents mounted on the triptycene skeleton. Herein, a unique interaction between electron‐rich substituents in the peri position and the silyl group located on the bridgehead sp3‐carbon is discussed on the example of 1,4‐dichloro‐9‐(p‐methoxyphenyl)‐silyltriptycene (TRPCl) which exists in solution in the form of two rotamers differing by dispositions, syn or anti, of the Si−CPh (the CPh atom is from the p‐methoxyphenyl group) bond against the peri‐Cl atom. For the first time, substantial differences between the Si−CPh bonds in these two dispositions are identified, based on indirect experimental and direct theoretical evidence. For these two orientations, the experimental 1J(Si,CPh) values differ by as much as 10 percent. The differences are explained in terms of effective electron density transfer from the peri‐Cl atom to the antibonding σ* orbitals of the Si−X bonds (X=H, CPh) oriented anti to that atom. The electronic effects are revealed by an NBO analysis. Connections of these observations with the notion of blue‐shifting hydrogen bonds are discussed.

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Section: Nmr Measurementsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Blue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density

et al. 2020

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“…On the one hand, the presence of steric congestion in the target triptycenes may cause some problems during its synthesis, but on the other hand it imparts unique properties. This was exactly the case with 1,4-dichloro-9-( p -methoxyphenyl)silyltriptycene (TRPCl), for which two synthetic routes were investigated in 2019 ( Scheme 4 ) [ 124 ].…”

Section: Progress In Triptycene Synthesis and Derivatizationmentioning

confidence: 99%

Triptycene Derivatives: From Their Synthesis to Their Unique Properties

2021

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Since the first preparation of triptycene, great progress has been made with respect to its synthesis and the understanding of its properties. Interest in triptycene-based systems is intense; in recent years, advances in the synthetic methodology and properties of new triptycenes have been reported by researchers from various fields of science. Here, an account of these new developments is given and placed in reference to earlier pivotal works that underpin the field. First, we discuss new approaches to the synthesis of new triptycenes. Progress in the regioselective synthesis of sterically demanding systems is discussed. The application of triptycenes in catalysis is also presented. Next, progress in the understanding of the relations between triptycene structures and their properties is discussed. The unique properties of triptycenes in the liquid and solid states are elaborated. Unique interactions, which involve triptycene molecular scaffolds, are presented. Molecular interactions within a triptycene unit, as well as between triptycenes or triptycenes and other molecules, are also evaluated. In particular, the summary of the synthesis and useful features will be helpful to researchers who are using triptycenes as building blocks in the chemical and materials sciences.

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Synthesis and structural characterization of exemplary silyl triptycenes

Abstract: Synthesis of sterically congested silyl triptycenes and their structural characterization via NMR, X-ray and PXRD are presented.

Cited by 2 publications

References 32 publications

Blue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density

Blue‐Shift Hydrogen Bonds in Silyltriptycene Derivatives: Antibonding σ* Orbitals of the Si−C Bond as Effective Acceptors of Electron Density

Triptycene Derivatives: From Their Synthesis to Their Unique Properties

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