As eries of highly emissive inert and chiral Cr III complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized.The helical [Cr(dqpR) 2 ] 3+ (dqp = 2,6-di(quinolin-8-yl)pyridine;R= OCH 3 ,B ro rC CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC.T he corresponding enantiomers show large g lum % 0.2 and high quantum yield of up to 17 %, whichaffordimportant CPL brightness of up to 170 m À1 cm À1 ,akey point for applications as chiral luminescent probes.M oreover,t he long-lived CP-NIR emission provided by these chromophores (ms range) in aqueous solution opens the way towardt he quantification of chiral targets in biological systems with timegated detection. Thus,s uch chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal-based complexes.

Purely organic shape-persistent chiral cages are designed through the use of rigid chiral axes. Covalent dimerization of a tripodal fragment bearing chiral allenes forms a molecular twisted prism with loop-like lateral edges presenting 10-fold chiroptical amplification compared to its isolated building blocks. The expected geometry of covalent organic helical cage (M,M)3 -1 was confirmed by X-ray crystal structure analysis. Comparison of the chiroptical responses of this shape-persistent molecular container with more flexible analogues highlights how the control of the conformational freedom of the molecule can be used to obtain molecular cages with strong chiroptical responses. Selective inclusion-complex formation with ferrocenium ions [(P,P)3 -1@Fc(+) ] was confirmed and quantified with HR-ESI-MS and NMR spectroscopy.

Chirality, a characteristic tool of molecular recognition in nature, is often a complement of redox active systems. Scientists, in their eagerness to mimic such sophistication, have designed numerous chiral systems based on molecular entities with cavities, such as macrocycles and cages. In an attempt to combine chirality and redox-active species, in this contribution we report the synthesis and detailed characterization of a chiral shapepersistent molecular cage based on the combination of enantiopure diethynylallenes and electron-rich bridged triarylamines, also known as N-heterotriangulenes. Its ability for chiral recognition in solution was revealed through UV/vis titrations with enantiopure helicenes.

Herein we describe a novel superhelicene structure consisting of three hexa-peri-hexabenzocoronene (HBC) units arranged in a helical geometry and creating two carbo[5]helicenes and a carbo[7]helicene. The central HBC bears a...