Octave-spanning emission across the visible spectrum from single crystalline 1,3,5,7-tetrakis-(p-methoxyphenyl)adamantane

Müller, Marius J.; Ziese, Ferdinand; Belz, Jürgen; Hüppe, Franziska; Gowrishankar, Saravanan; Bernhardt, Bastian; Schwan, Sebastian; Mollenhauer, Doreen; Schreiner, Peter R.; Volz, Kerstin; Sanna, Simone; Chatterjee, Sangam

doi:10.1364/ome.461427

Cited by 3 publications

(3 citation statements)

References 36 publications

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“…As a general feature, all clusters showing WLE are characterized by strong optical nonlinearities of second and third order, at least as strong as that of the crystalline ferroelectrics. 309,571,[642][643][644][645][646]650,651 The optical nonlinearities feature high peaks and low dips at which the optical coefficients are almost quenched, as seen by the example in Fig. 28 for the prototypical AdPh 4 .…”

Section: Optical Properties: Linear Optical Phenomena and Photocurren...mentioning

confidence: 95%

“…The optical response of a wide class of adamantane-based clusters and cluster aggregates has been calculated from rst principles in recent years. 309,571,[642][643][644][645] The calculations show that all adamantane-based clusters are characterized by a nonlinear optical response with the same structure, as long as they have the same ligand eld. For example, a prominent peak above 2 eV followed by a dip and a second peak is common to all adamantane-based cores with phenyl ligands.…”

Section: Optical Properties: Linear Optical Phenomena and Photocurren...mentioning

confidence: 99%

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Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Rinn,

Rojas-León,

Peerless

et al. 2024

Chem. Sci.

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Section: Optical Properties: Linear Optical Phenomena and Photocurren...mentioning

confidence: 95%

Section: Optical Properties: Linear Optical Phenomena and Photocurren...mentioning

confidence: 99%

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Rinn,

Rojas-León,

Peerless

et al. 2024

Chem. Sci.

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“…Adamantane is a highly symmetrical, rigid hydrocarbon that may be considered the smallest three-dimensional subunit of the diamond lattice. Substituted adamantanes are used to prepare cyclophanes, 1 2 3 4 to obtain materials for the storage and capture of small molecules from the liquid phase, 2 porous materials, 5,6 optical materials, 7 8 or as active pharmaceutical ingredients. 9 10 Further, adamantanes are interesting building blocks for erecting designed nanostructures 11 12 13 14 15 or hydrogen-bonded networks.…”

Section: Introductionmentioning

confidence: 99%

Kinetic or Thermodynamic Product? Case Studies on the Formation of Regioisomers of Tetraphenyladamantanes

Richert¹,

Frey²,

Berking³

2023

Synthesis

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Tetraaryldamantanes (TAAs) with alkoxyphenyl groups are interesting synthetic targets because they can act as crystallization chaperones for liquid compounds. Their carbon framework is set up by Friedel-Crafts alkylation, using adamantane-1,3,5,7-tetraol and anisole derivatives as starting materials. One successful chaperone is 1,3,5,7-tetrakis(2-bromo-4-methoxyphenyl)adamantane (TBro). This compound was initially considered the thermodynamic product of alkylation. We now report that exposure of TBro to strong Brønsted acid leads to its regioisomer 1,3,5,7-tetrakis(4-bromo-2-methoxyphenyl)adamantane (iTBro) as the dominant product, obtained in a yield of 68%, far surpassing the 20% yield reported earlier for TBro. We also investigated the reactions of 3-iodo-, 3-chloro-, and 3-fluoroanisole to the corresponding TAAs and obtained yields of 66%, 26% and 52% for the main regioisomer. While 3-iodoanisole gave the same regioisomer as bromoanisole, 3-chloroanisole gave complex mixtures and 3-fluoroanisole gave 1,3,5,7-tetrakis(2-fluoro-4-methoxyphenyl)-adamantane (TFM) in 52% yield as the main product. When mixtures of regioisomers were isomerized with an excess of triflic acid, the thermodynamic products were obtained in 76-91%. These results show how subtle effects govern the regioisomeric product distribution of aryladamantanes. They also help to make novel crystallization chaperones accessible in yields.

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Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

Gowrisankar,

Fokin,

Becker

et al. 2024

Eur J Org Chem

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Here we report our investigation of 1‐bromo‐3,5,7‐triphenyladamantane (1) and the elucidation of polymorphic crystals (1A and 1B) using single crystal X‐ray diffraction. In the monoclinic crystal system of 1A (P21/n), we observed CH−π interactions, while Br···Br interactions are absent. Conversely, the Br···Br interactions are an apparent factor in the formation of the monoclinic crystal system of 1B (R3). We compare our findings with 1,3,5,7‐tetraphenyladamantane (2), characterized by numerous CH−π interactions in the solid. Computational analyses were employed to investigate the interactions within the characteristic dimers present in the unit cells of 1A and 1B, including visualization of noncovalent interactions and the use of the atoms‐in‐molecules approach, and MO analysis. These support the notion of London dispersion (LD) dimer‐dimer interactions in 1A between the phenyl moieties, whereas 1B exhibits additional dimer‐dimer Br···Br contacts. In contrast, the crystals of 2 are exclusively held together by CH−π stacking LD interactions, a feature absent in the polymorphs of 1. Both polymorphic forms of 1 emit white light when subjected to 900 nm continuous wave laser irradiation, displaying a subtle blue shift compared to 2. The absence of CH−π stacking interactions between the dimers of 1 causes a small red‐shift in the emission spectrum.

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Octave-spanning emission across the visible spectrum from single crystalline 1,3,5,7-tetrakis-(p-methoxyphenyl)adamantane

Cited by 3 publications

References 36 publications

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Kinetic or Thermodynamic Product? Case Studies on the Formation of Regioisomers of Tetraphenyladamantanes

Polymorphism and White Light Emission of 1‐Bromo‐3,5,7‐triphenyladamantane Compared with 1,3,5,7‐Tetraphenyladamantane

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