Dithiafulvenyl‐Extended N‐Heterotriangulenes and Their Interaction with C₆₀: Cooperative Fluorescence

Abstract

We describe the synthesis as well as the electronic and photophysical characterization of novel N-heterotriangulene derivatives decorated with methoxycarbonyl-and methyl-sulfanyl-substituted dithiafulvenyl moieties. The association of these electron-richc ompounds with fullerene C 60 as electron acceptorw as investigated by meanso fp hotophysical, voltammetric,a nd mass spectrometric methods and rationalized by DFT calculations. Importantly,l ight-induced interactions between the dithiafulvene-substituted Nheterotriangulene bearing methoxycarbonyl substituents with C 60 leads to cooperative fluorescence. Quantitative Job plot analyses by means of fluorescences pectroscopy and voltammetry confirm a1 :1 association with binding constants in the order of 10 4 m À1.S upportive results for the supramolecular assembly of both N-heterotriangulenes with C 60 were obtainedb yE SI mass spectrometric investigations in the gas phase.

Bridged triarylboranes, ‐silanes, ‐amines, and ‐phosphines as minimalistic heteroatom‐containing polycyclic aromatic hydrocarbons: Progress and challenges

“…Yet another fascinating field of application for decorated bridged triarylamines was recently found in our group, when we realized that dithiafulvene‐decorated triarylamine 76 allowed for the formation of a 1:1 complex with fullerene C 60 with binding constants in the order of 10 4 M −1 (Figure ). DFT calculations and mass spectrometry corroborated the energetically favorable interactions in these complexes.…”

“…Structure of dithiafulvenyl‐extended bridged triarylamine 76 and fluorescence evolution of a mixture of 76 and C 60 in toluene during 12 h illumination at 350 nm together with the proposed molecular model for the formed 1:1 complex; adapted from Kivala and coworkers with permission from Wiley‐VCH…”

Charge and Spin Delocalization in Mixed-Valent Vinylruthenium–Triarylamine-Conjugates with Planarized Triarylamines

“…83−85 They also feature a reversible one-electron oxidation whose half-wave potential falls close to that of common TAs and depends on the substitution pattern of the attached aryl unit, as well as delocalized frontier orbitals with large contributions of the alkenyl ligand. 84,86−92 As an added benefit, the oxidation-induced shift of the CO stretching vibration of the metal-bonded carbonyl ligand as well as usually resolved hyperfine splittings of the unpaired electron spin to the 31 P nuclei of the phosphine ligands render the {Ru(CO)Cl-(P i Pr 3 ) 2 } complex entity (henceforth denoted as {Ru}) a sensitive indicator of the charge and spin density distributions over the alkenyl ligand and the metal ion. 85−89,93−108 The attachment of a TA tag to the alkenyl ligands of such ruthenium complexes has provided examples of electronically strongly coupled or even intrinsically delocalized asymmetric MV systems as is exemplified by the one-electron oxidized form of the complex {Ru}{−CHCH−C 6 H 4 N(C 6 H 4 -4-OMe) 2 } (Ru-TAOMe).…”

A Chiral Molecular Cage Comprising Diethynylallenes and N‐Heterotriangulenes for Enantioselective Recognition

“…[31] Regarding the implementation of triarylamines in both macrocyclic and cage structures, few examples can be tracked down in literature, [32][33][34][35][36][37][38][39] and even scarcer examples are found for their bridged analogues, N-HTAs, whose presence in complexing and sensing processes is limited. [40][41][42][43][44][45] Besides exploring uncharted waters, N-HTA are also of interest given their solid candidacy for next-generation optoelectronic materials, [46][47][48] and properties such as reversible redox chemistry. [49] Here we present the synthesis and full characterization of an organic covalent chiral cage composed of enantiopure DEAs and electron-rich dimethylmethylene-bridged N-HTAs together with the evidence for its enantioselective sensing ability in solution.…”

“… [31] Regarding the implementation of triarylamines in both macrocyclic and cage structures, few examples can be tracked down in literature,[ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ] and even scarcer examples are found for their bridged analogues, N ‐HTAs, whose presence in complexing and sensing processes is limited. [ 40 , 41 , 42 , 43 , 44 , 45 ] Besides exploring uncharted waters, N ‐HTA are also of interest given their solid candidacy for next‐generation optoelectronic materials,[ 46 , 47 , 48 ] and properties such as reversible redox chemistry. [49] …”