We present the up to now strongest chelating neutral pincer ligand for the simplest electrophile of chemistry, the proton. Two novel bisphosphazene proton sponges, 1,8-bis(trispyrrolidinophosphazenyl)naphthalene (TPPN) and its higher homologue P2-TPPN, were obtained via a Staudinger reaction and investigated concerning their structural features and basic properties by experimental and computational means. They exhibit experimental pK(BH)(+) values in acetonitrile of 32.3 and 42.1, respectively, exceeding the existing basicitiy record for proton sponges by more than 10 orders of magnitude. We show that Schwesinger's concept of homologization of phosphazene bases and Alder's concept of proton chelation in a constrained geometry regime of basic centers can be combined in the design of highly basic nonionic superbases of pincer type.

Experimental gas-phase superbasicity scale spanning 20 orders of magnitude and ranging from bicyclic guanidine 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene to triguanidinophosphazenes and P3 phosphazenes is presented together with solution basicity data in acetonitrile and tetrahydrofuran. The most basic compound in the scale-triguanidinophosphazene Et-N═P[N═C(NMe2)2]3-has the highest experimental gas-phase basicity of an organic base ever reported: 273.9 kcal mol(-1). The scale includes besides the higher homologues of classical superbasic phosphazenes and several guanidino-substituted phosphazenes also a number of recently introduced bisphosphazene and bis-guanidino proton sponges. This advancement was made possible by a newly designed Fourier transform ion cyclotron resonance (ICR) mass spectrometry setup with the unique ability to generate and control in the ICR cell sufficient vapor pressures of two delicate compounds having low volatility, which enables determining their basicity difference. The obtained experimental gas-phase and solution basicity data are analyzed in terms of structural and solvent effects and compared with data from theoretical calculations.

Dipyrrins serve as monovalent bidentate ligand molecules that coordinate to various cations. Their BF 2 complexes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene and its derivatives (BODIPYs), exhibit excellent photostability, strong light absorption, and high fluorescence quantum yield, thereby encouraging their application in various fields, e.g., as biological and biomedical fluorescent markers. Dipyrrin may also accept a wide variety of metal ions spontaneously. However, dipyrrin metal complexes have been disregarded from materials science research. This review article summarizes recent progress in bis(dipyrrinato)metal(II) and tris(dipyrrinato)metal(III) complexes from the viewpoint of materials chemistry. Section 2 describes a series of efforts aimed to realize intense luminescence superior to or comparable with that of BODIPYs. The spontaneous coordination of these complexes enables them to construct self-assembled nanoarchitectures, such as supramolecules and coordination polymers that form one-dimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks. Section 3 describes such alluring molecular superstructures. Section 4 discusses potential applications based on these nanoarchitectures, such as thermoelectric and photoelectric conversion. aimed to realize intense luminescence superior to or comparable with that of BODIPYs. Section 3 discusses the selfassembly of bis and tris(dipyrrinato)metal complexes, which results in the formation of alluring nanoarchitectures, such as supramolecules and coordination polymers giving rise to onedimensional nanowires, two-dimensional nanosheets, and metal-organic frameworks (MOFs) and porous coordination polymers (PCPs). Section 4 describes potential applications based on these nanoarchitectures. Pursuit of bright luminescenceA plain BODIPY shows intense absorption and bright fluorescence at approximately 500 nm, which are derived from the 1 π-π * transition of the dipyrrinato ligand. 5-16 The absorption and fluorescence may be redshifted upon the introduction of substituents on the dipyrrinato ligand, covering the region 500-900 nm. BODIPYs are good fluorophores even in polar solvents such as water. In sharp contrast, dipyrrin metal complexes have long been believed to be non-luminescent or weakly luminescent. This drawback seriously reduces the value of dipyrrinato-metal complexes in applications in which they serve, for example, as photosensitizers. In this section, the authors concentrate on efforts to improve the luminescent ability of bis and tris(bisdipyrrinato)metal complexes. For comprehensive knowledge on the whole types of luminescent dipyrrinato-metal complexes (i.e. mono(dipyrrinato)metal complexes with ancillary ligands other than dipyrrins), please see a comprehensive review article contributed by Baudron. 2

Al(OCArF3)3 (ArF = C6F5) – a readily accessible, adduct free and highly stable Lewis superacid with an extreme fluoride ion affinity to store in your glove box!

One-dimensional (1D) coordination polymers (CPs) experiences limitations in exfoliation into individual strands, which hamper their utility as functional 1D nanomaterials. Here we synthesize chiral 1D-CPs that feature the bis(dipyrrinato)zinc(II) complex motif. They can be exfoliated into single strands upon sonication in organic media, retaining lengths of up to 3.19 μm (ca. 2600 monomer units). Their chiroptical structure allows the exfoliated wires to show circularly polarized luminescence at an intensity 5.9 times that of reference monomer complexes.