Elektronentransfer um eine molekulare Ecke

Spirobifluorene derivatives find use in many end-user applications. Therefore, furthere xpansiono f their scopei st he focus of many research studies. However,a lthough the optical properties of spirobifluorenes can be greatly tuned through incorporation of metal complexes,t od ate, spirobifluorene metallaaromatics remain unknown. Ta king advantage of the versatility of our methodologyf or the synthesis of metallaaromatic systems, this work reports the first metallaaromatic spirobifluorene compound. The presence of an Ir atom was found to redshift the absorption maximum by ca. 1.1 eV comparedt o bare spirobifluorene. Additionally,X -ray analysisa sw ell as anisotropy of the current-induced density calculations revealed this compound to be of aromatic nature.T he high stabilityi ns olution, solids tate, under air,a nd at high temperature, as well as distinct optical properties of this new class of compounds are expected to open new frontiers for chiroptical and optoelectronica pplications.

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Spirobifluorene Metallaaromatics

Arias‐Coronado

Pereira-Cameselle

Ozcelik

et al. 2019

Chemistry A European J

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Shortcuts for Electron‐Transfer through the Secondary Structure of Helical Oligo‐1,2‐Naphthylenes

Castrogiovanni

Herr

Larsen

et al. 2019

Chemistry A European J

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Atropisomeric1 ,2-naphthylene scaffolds provide access to donor-acceptor compounds with helical oligomerbased bridges,a nd transient absorption studies revealed a highly unusuald ependenceo ft he electron-transfer rate on oligomer length, whichi sd ue to their well-defined secondary structure. Close noncovalent intramolecular contacts enable shortcuts for electron transfer that would otherwise have to occur over longerd istances along covalentp athways, reminiscent of the behavior seen for certain proteins. The simplistic pictureo ft ube-like electron transferc an de-scribe this superpositiono fd ifferent pathways including both the covalenth elical backbone, as well as noncovalent contacts, contrasting the wire-like behavior reportedm any times before for more conventional molecular bridges. The exquisite control over the molecular architecture, achievable with the configurationally stable and topologically defined 1,2-naphthylene-baseds caffolds, is of key importancef or the tube-like electron transfer behavior.O ur insights are relevant for the emerging field of multidimensional electron transfer and for possible future applications in molecular electronics.Scheme1.(a) Electron transfer (ET) through linear wires;( b) ET across the covalent backboneofah elical structure;(c) conformational flexibility complicates the assessment of the relative importanceo fc ovalent versus noncovalentlypathways;and (d) ET pathway involving noncovalent contacts in ahelical structure.Scheme2.(a) Donor-acceptor dyads synthesized and investigated in this work;and (b) space-filling modelo ft he dyad with n = 3( compound W3).

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Elektronentransfer um eine molekulare Ecke

Cited by 2 publications

References 90 publications

Spirobifluorene Metallaaromatics

Spirobifluorene Metallaaromatics

Shortcuts for Electron‐Transfer through the Secondary Structure of Helical Oligo‐1,2‐Naphthylenes

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