While materials based on organic molecules usually have either superior optoelectronic or superior chiral properties, the combination of both is scarce. Here, a crystalline chiroptical film based on porphyrin with homochiral side groups is presented. While the dissolved molecule has a planar, thus, achiral porphyrin core, upon assembly in a metal-organic framework (MOF) film, the porphyrin core is twisted and chiral. The close packing and the crystalline order of the porphyrin cores in the MOF film also results in excellent optoelectronic properties. By exciting the Soret band of porphyrin, efficient photoconduction with a high On-Off-ratio is realized. More important, handednessdependent circularly-polarized-light photoconduction with a dissymmetry factor g of 4.3 × 10 À 4 is obtained. We foresee the combination of such assembly-induced chirality with the rich porphyrin chemistry will enable a plethora of organic materials with exceptional chiral and optoelectronic properties.
Herein we present the first synthesis of bicyclo[1.1.1]pentyl (BCP) sulfoximines from the corresponding sulfides. Both BCPs and sulfoximines are bioisosteres used in medicinal chemistry and therefore desirable motifs. The access to BCP sulfides was enabled by the thiol addition to [1.1.1]propellane as published before. A broad scope with specific limitations was discovered for the sulfoximination. To diversify the sulfoximines, N‐acylations and N‐arylations were performed. As the N‐arylation was low yielding we optimized the copper(I) catalyzed reaction. A wide range of aryl iodides could be deployed and competitive reactions showed that aryl bromides react equally fast. In a scale‐up we prepared a suitable precursor for a BCP drug analogue. In this work several molecular structures could be determined by single‐crystal X‐ray diffraction.
Während Materialien auf der Basis organischer Moleküle in der Regel entweder exzellente optoelektronische oder exzellente chirale Eigenschaften aufweisen, ist die Kombination aus beiden selten. Hier wird ein kristalliner chiroptischer Film auf Basis von Porphyrin mit homochiralen Seitengruppen vorgestellt. Während das gelöste Molekül einen planaren, also achiralen Porphyrin-Kern hat, ist der Porphyrin-Kern beim Einbau in einen metallorganischen Gerüstfilm (MOF) verdreht und chiral. Die dichte Packung und die kristalline Ordnung der Porphyrinmoleküle im MOF-Film führen auch zu hervorragenden optoelektronischen Eigenschaften. Durch Anregung des Soret-Bandes von Porphyrin wird eine effiziente Fotoleitung mit einem hohen An-Aus-Verhältnis erreicht. Noch wichtiger ist, dass eine von der Händigkeit abhängige Fotoleitfähigkeit von zirkular polarisiertem Licht mit einem Dissymmetriefaktor g von 4.3 × 10 À 4 erreicht wird. Wir gehen davon aus, dass die Kombination solcher chiralen Filme mit der reichhaltigen Porphyrinchemie eine Fülle von organischen Materialien mit außergewöhnlichen chiralen und optoelektronischen Eigenschaften ermöglichen wird.
A chiral metal‐organic framework film with optoelectronic properties based on functionalized porphyrin molecules is presented by Mariana Kozlowska, Lars Heinke et al. in their Research Article (e202217377). While the porphyrin molecules in solution (red) are planar, as common porphyrin, the porphyrin cores are twisted and chiral upon assembly in the metal‐organic framework. The close packing and the crystalline order of the porphyrin cores in the film result in excellent photoconduction properties and sensitivity to circularly polarized light.
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