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Abstract Reactions of the Ir^Vhydride [^MeBDI^Dipp]IrH₄{BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐iPr₂C₆H₃} with E[N(SiMe₃)₂]₂(E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([^MeBDI^Dipp]IrH)₂(μ₂‐E)₂in good yields. Moreover, ([^MeBDI^Dipp]IrH)₂(μ₂‐Ge)₂was formed in situ from thermal decomposition of [^MeBDI^Dipp]Ir(H)₂Ge[N(SiMe₃)₂]₂. These reactions are accompanied by liberation of HN(SiMe₃)₂and H₂through the apparent cleavage of an E−N(SiMe₃)₂bond by Ir−H. In a reversal of this process, ([^MeBDI^Dipp]IrH)₂(μ₂‐E)₂reacted with excess H₂to regenerate [^MeBDI^Dipp]IrH₄. Varying the concentrations of reactants led to formation of the trimeric ([^MeBDI^Dipp]IrH₂)₃(μ₂‐E)₃. The further scope of this synthetic route was investigated with group 15 amides, and ([^MeBDI^Dipp]IrH)₂(μ₂‐Bi)₂was prepared by the reaction of [^MeBDI^Dipp]IrH₄with Bi(NMe₂)₃or Bi(OtBu)₃to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir₂E₂(E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir₂Bi₂is characterized as having a closed‐shell singlet ground state. 

Abstract Self‐sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by‐design molecules. However, most studies have been focused on non‐covalent systems, and using self‐sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self‐sorting behavior observed in the transformation between spiroborate‐linked well‐defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single‐crystal X‐ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi‐component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape‐persistent molecular cage, driven by dynamic covalent self‐sorting. This study will further guide the design of spiroborate‐based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems. 

Abstract Polarimetric infrared (IR) detection bolsters IR thermography by leveraging the polarization of light. Optical anisotropy, i.e., birefringence and dichroism, can be leveraged to achieve polarimetric detection. Recently, giant optical anisotropy is discovered in quasi‐1D narrow‐bandgap hexagonal perovskite sulfides, A_1+xTiS₃, specifically BaTiS₃and Sr_9/8TiS₃. In these materials, the critical role of atomic‐scale structure modulations in the unconventional electrical, optical, and thermal properties raises the broader question of the nature of other materials that belong to this family. To address this issue, for the first time, high‐quality single crystals of a largely unexplored member of the A_1+xTiX₃(X = S, Se) family, BaTiSe₃are synthesized. Single‐crystal X‐ray diffraction determined the room‐temperature structure with theP31cspace group, which is a superstructure of the earlier reportedP6₃/mmcstructure. The crystal structure of BaTiSe₃features antiparallelc‐axis displacements similar to but of lower symmetry than BaTiS₃, verified by the polarization dependent Raman spectroscopy. Fourier transform infrared (FTIR) spectroscopy is used to characterize the optical anisotropy of BaTiSe₃, whose refractive index along the ordinary (E⊥c) and extraordinary (E‖c) optical axes is quantitatively determined by combining ellipsometry studies with FTIR. With a giant birefringence Δn∼ 0.9, BaTiSe₃emerges as a new candidate for miniaturized birefringent optics for mid‐wave infrared to long‐wave infrared imaging.