Pt(II) Tetrafacial Barrel with Aggregation-Induced Emission for Sensing.

A new tetraphenylpyrazine-based tetraimidazole ligand (L) was synthesized and used for subcomponent self-assembly with cis-(tmeda)Pd(NO3)2 and cis-Pt(PEt3)2(OTf)2, leading to the formation of two tetrafacial barrels [Pd8L4(tmeda)8](NO3)16 (1) and [Pt8L4(PEt3)16](OTf)16 (2), respectively. Although ligand L is aggregation-induced emission (AIE) active, barrel 2 showed a magnificently higher AIE activity than ligand L, while 1 failed to retain the AIE properties of the ligand. Pd(II) barrel 1, undergoing an aggregation-caused quenching (ACQ) phenomenon, nullified the AIE activity of the ligand to be used in the photophysical application. The enhanced emission in the aggregated state of Pt(II) barrel 2 was used for the recognition of picric acid (PA), which is explosive in nature and one of the groundwater contaminants in landmine areas. The recognition of picric acid was found to be selective in comparison with that of other nitroaromatic compounds (NACs), which could be attributed to ground-state complex formation and resonance energy transfer between picric acid and barrel 2. The use of new AIE-active assembly 2 for selective detection of PA with a low detection limit is noteworthy.

An Adaptable Water-Soluble Molecular Boat for Selective Separation of Phenanthrene from Isomeric Anthracene.

Anthracene crude oil is a common source of phenanthrene for its industrial use. The isolation of phenanthrene from this source is a challenging task due to very similar physical properties to its isomer anthracene. We report here a water-soluble Pd(II) molecular boat (MB1) with unusual structural topology that was obtained by assembling a flexible tetrapyridyl donor (L) with a cis-Pd(II) acceptor. The flexible backbone of the boat enabled it to breathe in the presence of a guest optimizing the fit within the cavity. The boat binds phenanthrene more strongly than anthracene, which enabled separation of phenanthrene with an >98% purity from an equimolar mixture of the two isomers using MB1 as an extracting agent. MB1 represents a unique example of a coordination receptor suitable for selective aqueous extraction of phenanthrene from anthracene with reusability of several cycles.

Annulating thiazolium cations via a direct double C-H activation strategy: Rh-N,S-heterocyclic carbene is the key.

Herein we show how metal-N,S-heterocyclic carbene intermediates are conveniently generated and utilized for the first time to construct N,S doubly-doped cationic conjugated tricyclic organic molecules which exhibit tuneable emission. The chemistry proceeds via direct double C-H activation followed by an annulative π-extension pathway.