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Abstract Multiplex imaging in the second near‐infrared window (NIR‐II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real‐time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric Ln^III/Ga^IIImetallacrowns bearing Ru^IIpolypyridyl complexes,LnRu‐3(Ln=Y^III, Yb^III, Nd^III, Er^III). Relaxed structures ofYRu‐3in the ground and the excited electronic states have been calculated using dispersion‐corrected density functional theory methods. Detailed photophysical studies ofLnRu‐3have demonstrated that characteristic emission signals of Yb^III, Nd^IIIand Er^IIIin the NIR‐II range can be sensitized upon excitation in the visible range through Ru^II‐centered metal‐to‐ligand charge transfer (MLCT) states. We have also showed that these NIR‐II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue‐mimicking phantoms. This work opens unprecedented perspectives for NIR‐II multiplex imaging using Ln^III‐based molecular compounds. 

Abstract By combining advantages of two series of lanthanide(III)/zinc(II) metallacrowns (MCs) assembled using pyrazine‐ (pyzHA²⁻) and quinoxaline‐ (quinoHA²⁻) hydroximate building blocks ligands, we created here water‐soluble mixed‐ligand MCs with extended absorption to the visible range. The Yb^IIIanalogue demonstrated improved photophysical properties in the near‐infrared (NIR) range in cell culture media, facilitating its application for NIR optical imaging in living HeLa cells. 

Abstract Seven dimeric metallacrowns (MC) based on Ln[12‐MC_M(III)N(shi)‐4], where Ln^III=Dy, Ho, Yb, or Y, M^III=Mn or Ga, and shi³⁻is salicylhydroximate, have been synthesized and characterized by single‐crystal X‐ray diffraction, and for the dysprosium‐manganese dimers, the magnetic properties have been measured. In each dimer two Ln[12‐MC_M(III)N(shi)‐4] units are linked by four bridging dicarboxylate anions (isophthalate, trimesate, dinicotinate, or 2,2′‐dithiodibenzoate). Three different countercations (sodium, gallium(III), or pyridinium) were used to maintain charge balance of the dimer. While pyridinium does not bind to the dimer, the choice of the dicarboxylate dictates where the countercations Na⁺or Ga^IIIbind. With isophthalate and trimesate, the sodium ion binds to the central MC cavity opposite of the Ln^III, and with dinicotinate the sodium or gallium(III) ions bind to the pyridyl nitrogen of the dinicotinate. All three Dy₂Mn₈dimers exhibit an out‐of‐phase magnetic susceptibility signal consistent with a shallow barrier to magnetization relaxation. 

The fine tuning of CIE coordinates was demonstrated in a series of molecular tetrachroic chromophores, Dy³⁺/Ga³⁺metallacrowns, through modifications of the symmetry around Dy³⁺and the nature of the organic ligands.