Two isostructural pairs of supramolecular iodoantimonate(III) and iodobismuthate(III) complexes with I₂ units “trapped” in solid state via halogen bonding—Cat₃[[M₂I₉](I₂)} (Cat = tetramethylammonium and 1-methylpyridinium, M = Sb(III) and Bi(III)) were prepared. For all compounds, values of optical band gaps were determined, together with thermal stability; the complexes were additionally characterized by Raman spectroscopy.

Nine heterometallic iodobismuthates with the general formula Cat₂{[Bi₂M₂I₁₀}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {Bi₂I₁₀} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C. Optical band gaps (E_g), estimated at room temperature via diffuse reflectance measurements, range from 1.81 to 2.03 eV. Thermally induced changes in optical behavior (thermochromism) for compounds 1–9 were recorded, and general correlations were established. The thermal dependence of E_g appears to be close to linear for all studied compounds.

Supramolecular dichloro-chlorostannate(IV) and -plumbate(IV) complexes (Me₃NH)₂{[MCl₆]Cl₂} (M = Sn (1), Pb (2)) feature dichlorine units incorporated into a halometalate framework. Both compounds were characterized by X-ray diffractometry and Raman spectroscopy.

Reactions between bromoselenate(IV)-containing solutions, dibromine and salts of pyridinium-family organic cations resulted in structurally diverse, bromine-rich polybromine-bromoselenates(IV): (4-MePyH)₅[Se₂Br₉][SeBr₆](Br₃)₂ (1), (2-MePyH)₂{[SeBr₆](Br₂)} (2), (PyH)₂{[SeBr₅]Br(Br₂)₂} (3), (1-MePy)₂{[SeBr₆](Br₂)} (4). The compounds feature halogen and (in the case of 3) chalcogen bonding in solid state, resulting in formation of supramolecular architectures of different dimensionality. DFT calculations allowed estimation of the energies of non-covalent interactions in 1–4; additionally, characterization by Raman spectroscopy was performed.

Three supramolecular bromostannates(IV) with “trapped” diiodine molecules, Cat₂{[SnBr₆](I₂)} (Cat = Me₄N⁺ (1), 1-MePy⁺ (2) and 4-MePyH (3)), were synthesized. In all cases, I₂ linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles 1–3 were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The latter indicates that 1–3 are narrow band gap semiconductors.

The first examples of Bi(III) and Sb(III) halide compounds combined with a photoswitchable ruthenium nitrosyl unit are reported. The structures of [RuNOPy₄Br]₄[Sb₂Br₈][Sb₃Br₁₂]₂ (1) and (H₃O)[RuNOPy₄Br]₄[Bi₂Br₉]₃·3H₂O (2) were determined by X-ray diffraction, and exhibit three different structural types of group 15 halometalates. Low-temperature IR-spectroscopy measurements reveal that the irradiation of 1 at 365 nm switches a stable Ru–NO (GS) unit to a metastable Ru–ON (MS1) linkage. Moreover, the light excitation of 2 at 365 or 405 nm induces the additional formation of a side-bond isomer Ru-η²-(NO) (MS2). The reverse reactions MS1/MS2 → GS can be induced by red–infrared light irradiation or by heating at temperatures >200 K. The obtained synthetic and spectroscopic data open the way for the preparation of hybrid halide complexes with a variety of photoswitchable complexes (NO₂, SO₂, N₂, etc.), and give an insight into the behavior of light-induced species embedded in polynuclear halides.