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We report a structure-property study on phosphoryl-bridged viologen analogues with a remarkably low reduction threshold. Utilizing different benzyl groups for N-quaternization, we were able to confirm the p-benzyl substituent effect on the electronic tunability of the system while maintaining the characteristic chromic response of viologens with two fully reversible one-electron reductions. Due to the considerably increased electron-acceptor properties of the phosphoryl-bridged bipyridine precursor, N-benzylation was found to be very challenging and required the development of new synthetic strategies toward the target viologen species. This study also introduces a new and convenient way for the anion exchange of viologen systems by utilizing methyl triflate. Finally, the practical utility of the new species was verified in simplified proof-of-concept electrochromic devices.

A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a π* → π transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled 1D fibrous structures on the micrometer scale.

A simple and representative procedure for the synthesis of N,N'-diarylated phosphaviologens directly from both electron-rich and electron-poor diaryliodonium salts and 2,7-diazadibenzophosphole oxide is reported. The latter are electron-deficient congeners of the widely utilized N,N'-disubstituted 4,4'-bipyridinium cations, also known as viologens, that proved to be inaccessible by the classical two-step route. The single-step preparation method for phosphaviologens described herein could be extended to genuine viologens but reached its limit when sterically demanding diaryliodonium salts were used. The studied phosphaviologens feature a significantly lowered reduction threshold as compared to all other (phospha)viologens known to date due to the combination of an extended π-system with an electron deficient phosphole core. In addition, a considerably smaller HOMO-LUMO gap was observed due to efficient π-delocalization across the phosphaviologen core, as well as the N-aryl substituents, which was corroborated by quantum chemical calculations. Detailed characterizations of the singly reduced radical species by EPR spectroscopy and DFT calculations verified delocalization of the radical over the extended π-system. Finally, to gain deeper insight into the suitability of the new compounds as electroactive and electrochromic materials, multicolored proof-of-concept electrochomic devices were manufactured.

To obtain mechanistic insight, detailed studies of the intriguing "spontaneous" ambient temperature ring-opening polymerization (ROP) of tin-bridged [1]ferrocenophanes Fe(eta-C(5)H(4))(2)SnR(2) 3a (R = t-Bu) and 3b (R = Mes) in solution have been performed. The investigations explored the influence of non-nucleophilic additives such as radicals and radical traps, neutral and anionic nucleophiles, Lewis acids, protic species, and other cationic electrophiles. Significantly, two novel methodologies and mechanisms for the ROP of strained [1]ferrocenophanes are proposed based on this study. First, as the addition of amine nucleophiles such as pyridine was found to strongly accelerate the polymerization rate in solution, a new nucleophilicallyassisted ROP methodology was proposed. This operates at ambient temperature in solution even in the presence of chlorosilanes but, unlike the anionic polymerization of ferrocenophanes, does not involve cyclopentadienyl anions. Second, the addition of small quantities of the electrophilic species H(+) and Bu(3)Sn(+) was found to lead to a cationic ROP process. These studies suggest that the "spontaneous" ROP of tin-bridged [1]ferrocenophanes may be a consequence of the presence of spurious, trace quantities of Lewis basic or acidic impurities. The new ROP mechanisms reported are likely to be of general significance for the ROP of other metallocenophanes (e.g., for thermal ROP in the melt) and for other metallacycles containing group 14 elements.

Phosphoranylidene carbenoids Mes*-P(E)C(X){Li(THF)3} (E = C(SiMe3)2, NMes*; X = F, Cl, Br, 10−13, 15) were synthesized and their molecular structures characterized by low-temperature X-ray diffractometry and multinuclear NMR studies. The experiments confirm the presence of monomeric molecules with THF-solvated metal atoms in both solution and solid state. The solid carbenoids display elongated C−X bonds and distortions of carbon bond angles which represent typical features of carbenoids and suggest an interpretation of the bonding situation as a contact ion pair between a carbanion and a solvated metal cation. This is corroborated by NMR studies which show that the dynamic exchange between the two components in solution can be directly monitored in 2D 6Li,31P shift correlations. While structural and spectroscopic data give no evidence for a continuously increasing stability between F-, Cl-, or Br-substituted carbenoids, they reveal the presence of marked structural differences between the E/Z-isomers 10 a...

A series of new amphiphilic phosphonium materials that combine the electronic features of phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a "closed" and "open" form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD). The studies revealed that both conjugated backbones and counteranions work together to organize the systems into different morphologies (liquid crystal/soft crystal). Dithieno[3,2-b:2',3'-d]phosphole-based compounds exhibit enhanced emission in the solid state and at low temperature in solution due to aggregation-induced enhanced emission (AIEE). Photoinduced electron transfer (PET) induced via the alkoxybenzyl group at the phosphonium center in the fused-ring systems can be effectively suppressed through intermolecular charge transfer (ICT) processes within the main scaffold of a nonfused system, which was confirmed by static and dynamic fluorescence spectroscopy. The dynamic features of these new materials also endow the systems with external-stimuli responsive photophysical properties that can be triggered by temperature and/or mechanical forces.

New ladder-type, phosphorus- and sulfur-based heterotetracenes were synthesized, which allowed the engineering of the materials' properties by exploitation of the different reactivities between sulfur and phosphorus. (31)P NMR spectroscopy and X-ray crystallographic studies revealed that the different electronic effects of the secondary heteroatom, sulfur, influence not only the conjugation in the heterotetracene core but also the behavior of the phosphorus center. UV-vis and fluorescence spectroscopy showed that the scaffold's band gap is mainly controlled by the electronic nature of sulfur, while the fluorescence quantum yield highly depends on the electronic nature of phosphorus. Cyclic voltammetry indicated that the redox properties of the system could be altered by selective modification of the respective heteroatom (oxidation of sulfur and/or functionalization of trivalent phosphorus). Importantly, oxidation of the phosphorus center results in enhanced reduction features of the heterotetracene system, and oxidation of the sulfur center further enhances the electron acceptor character of the core. Theoretical calculations provided insights on both selectivity of phosphorus chemistry and communication between the two heteroatoms (sulfur and phosphorus). Macroscopic self-organization of the heterotetracenes was observed when the tetracene core is functionalized with pendant functional groups. Preliminary results showed that extension of the molecule with an alkyl chain along the long axis of molecules induces the formation of 1D microfibers, which was confirmed by fluorescence microscopy and scanning electron microscopy.