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We report a highly contorted phosphaquinoid by substituting one of the exocyclic C C bonds of an anthraquinodimethane unit with a phosphaalkene unit (–C P-Mes*, Mes* = 2,4,6-tri-tbutylbenzene) and end-capping the opposite terminus with ‘ C(Fc)Ph’. Both isomers (E,Z) exhibit butterfly-like distortion of the anthracene core and demonstrate remarkable stability towards air and moisture.

In this study, we present the synthesis and analysis of a novel, air-stable, and solvent-resistant phosphaalkene switch. Using this symmetric switch, we have demonstrated degenerate photoisomerization experimentally for the first time. With a combination of photochemical-exchange NMR spectroscopy, ultrafast transient absorption spectroscopy, and quantum chemical calculations, we elucidate the isomerization mechanism of this symmetric phosphaalkene, comparing it to two other known molecules belonging to this class. Our findings highlight the critical role of the isolobal analogy between C=P and C=C bonds in governing nanoscale molecular motion and break new ground for our understanding of light-induced molecular processes in symmetric heteroalkene systems.

This experimental and theoretical study illustrates how phosphaalkenes, which are isolobal to alkenes, can utilize a variety of external triggers for molecular switching. The E/Z isomerization of a truxene-based phosphaalkene, i. e. TruxC=P-Mes* (Mes*=2,4,6-tris-t-butyl-benzene), is accomplished by irradiation, metal coordination, or deprotonation of the truxene core. The reversible and quantitative Z/E double bond isomerization by gold(I) coordination/decoordination of the phosphorous lone pair represents a novel fuelling strategy for molecular switches.

An indolizidine alkaloid, (-)-8a-epi-lentiginosine was synthesized from D-glucose using the Pd-BiPhePhos catalyzed intramolecular Tsuji-Trost reaction of non-derivatized allylic alcohol as a key construction of the hydroxylated pyrrolidine ring to give the desired product in good yield and high stereospecificity (dr = 97:3). The absolute configuration and structure of (-)-8a-epi-lentiginosine were confirmed by NMR and X-ray crystal structure analysis. The crystal structure of (-)-8a-epi-lentiginosne showed the envelope conformation of the five-membered ring, which is an N-atom in the endo-position, and the fused six-membered ring adopts a chair conformation similar to the DFT optimized structure. The solid-state packing is dominated by a 1D-hydrogen-bonded network along the a-axis involving both hydroxyl groups and the amine. The large HOMO-LUMO energy gap indicated the high stability of the compound.

A series of 2,1,3-benzothiadiazole–Au(I)–L complexes have been synthesised, structurally characterised and investigated for their photophysical properties. These are the first organometallic Au(I) complexes containing a C–Au bond on the highly electron-deficient benzothiadiazole unit. The complexes exhibit solution-phase phosphorescence at room temperature, assigned to the intrinsic triplet state of the benzothiadiazole unit that is efficently populated through its attachment to gold. Comparison with routinely reported Au(I) complexes, which include intervening alkenyl linkers, suggests that previous assignments of their phosphorescence as ¹π → π*(CCR) might be incomplete. Our observations affirm that, in addition to the heavy atom effect, breaking symmetry in the involved aryl motif may be of importance in controlling the luminescence properties.

The phytochemical investigation of the leaves and the roots of Suregada procera afforded the new ent-abietane diterpenoid sureproceriolide A (1) along with the known secondary metabolites 8,14β:11,12α-diepoxy-13(15)-abietane-16,12-olid (2), jolkinolide A (3), jolkinolide E (4), ent-pimara-8(14),15-dien-19-oic acid (5), sitosterol (6), oleana-9(11):12-dien-3β-ol (7), and oleic acid (8). Their structures were elucidated by NMR spectroscopic and mass spectrometric analyses, and the structure of jolkinolide A (3) was confirmed by single-crystal X-ray diffraction analysis. Sureproceriolide A (1) showed modest activity against the Gram-positive bacterium Staphylococcus lugdunensis (MIC = 31.44 μM), and sitosterol (6) against the Gram-negative bacterium Porphyromonas gingivalis (IC₅₀ = 45.37 μM). Jolkinolide A (3) and E (4) as well as sitosterol (6) inhibited the release of NOS (IMR-90 cells), TNF-α (HaCaT cells) and NF-κB (HaCaT cells), with IC₅₀ values of 0.43, 3.21, and 10.32 μM, respectively. Compound 6 showed antitumoral activity against SK-MEL-28 (IC₅₀ = 20.66 μM) and CCD-13Lu (IC₅₀ = 24.70 μM) cell lines, with no cytotoxic effect against the prostate cells PrEC (CC₅₀ > 300 μM).

Despite growing interest in 2,1,3-benzothiadiazole (BTD) as an integral component of many functional molecules, methods for the functionalization of its benzenoid ring have remained limited, and many even simply decorated BTDs have required de novo synthesis. We show that regioselective Ir-catalyzed C–H borylation allows access to versatile 5-boryl or 4,6-diboryl BTD building blocks, which undergo functionalization at the C4, C5, C6, and C7 positions. The optimization and regioselectivity of C–H borylation are discussed. A broad reaction scope is presented, encompassing ipso substitution at the C–B bond, the first examples of ortho-directed C–H functionalization of BTD, ring closing reactions to generate fused ring systems, as well as the generation and capture reactions of novel BTD-based heteroarynes. The regioselectivity of the latter is discussed with reference to the Aryne Distortion Model.

The stepwise reduction of the highly contorted truxene-based triphosphaalkene 1 using KC8 led to the isolation of mono-, di-, and tri-anionic species. The solid-state molecular structures of mono- and diradical anionic species were elucidated by single crystal X-ray diffractions, revealing elongated P−C bonds and a pronounced “indene” aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open-shell electronic configuration of both the diradical and triradical species—an observation unprecedented in any previously reported phosphorous-based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34 % each), with a minor contribution from the third phosphorous (0.13 %), while the trianion demonstrates a uniform distribution of spin density (~30 %) across each phosphorous atom.

Thiele's Hydrocarbons (THs) featuring a 9,10-anthrylene core with switchable geometric and electronic configurations offer exciting possibilities in advanced functional materials. Despite significant advances in main group-based diradicaloids in contemporary chemistry, main group THs containing an anthrylene cores have remained elusive, primarily due to the lack of straightforward synthetic strategies and the inherent high reactivity of these species. In this study, we utilize an anthracene-based phosphine synthon to demonstrate, for the first time, a facile and high-yielding synthetic strategy for robust P-functionalized overcrowded ethylenes (OCEs) within the TH family. These OCEs feature a non-symmetric environment, incorporating (thio) xanthyl and phosphaalkene termini. We systematically probe the electronic structures of these derivatives to illustrate the impact of the isolobal phosphaalkene motif on the quinoidal/diradicaloid character. Notably, the compounds exhibit dynamic redox behavior, leading to orthogonally twisted conformational changes upon oxidation, with a kinetically locked redox-couple.

Heterofulvenes based on isolobal substitution of carbon fragments by (heavier) main group motifs provide a rich source of structurally interesting building blocks with electronic situations that can vastly differ from all-carbon congeners. Group 13, heavier 14 & 16 fulvenes are rare and pose significant stability challenges, while group 15 derivatives, particularly phosphorus and arsenic, have led to many derivatives with intriguing opto-electronic properties.