The search for bifunctional materials showing synergies between spin crossover (SCO) and luminescence has attracted substantial interest since they could be promising platforms for new switching electronic and optical technologies. In this context, we present the first three-dimensional Fe^II Hofmann-type coordination polymer exhibiting SCO properties and luminescence. The complex {Fe^II(bpben)[Au(CN)₂]}@pyr (bpben = 1,4-bis(4-pyridyl)benzene) functionalized with pyrene (pyr) guests undergoes a cooperative multi-step SCO, which has been investigated by single crystal X-ray diffraction, single crystal UV-Vis absorption spectroscopy, and magnetic and calorimetric measurements. The resulting fluorescence from pyrene and exciplex emissions are controlled by the thermal and light irradiation (LIESST effect) dependence of the high/low-spin state population of Fe^II. Conversely, the SCO can be tracked by monitoring the fluorescence emission. This ON–OFF interplay between SCO and luminescence combined with the amenability of Hofmann-type materials to be processed at the nano-scale may be relevant for the generation of SCO-based sensors, actuators and spintronic devices.

The research of new multifunctional materials, as those undergoing spin crossover (SCO) and luminescent properties, is extremely important in the development of further optical and electronic switching devices. As a new step towards this ambitious aim, the coupling of SCO and fluorescence is presented here following two main strategies: whether the fluorescent agent is integrated as a part of the main structure of a 3D SCO coordination polymer {Fe^II(bpan)[M^I(CN)₂]₂} (bpan = bis(4-pyridyl)anthracene, M^I = Ag (FebpanAg), Au (FebpanAu)) or is a guest molecule inserted within the cavities of the 3D switchable framework {Fe^II(bpb)[M^I(CN)₂]₂}·pyrene (bpb = bis(4-pyridyl)butadiyne, M^I = Ag (FebpbAg·Pyr), Au (FebpbAu·Pyr)). The magnetic, calorimetric, structural, UV-Vis absorption and fluorescent characterizations were performed confirming the occurrence of a SCO-fluorescence interplay in the studied compounds. Moreover, the relevance of the intrinsic or extrinsic nature of the luminescence on the efficiency of the interplay is discussed on the basis of the available information.

The property of persistent luminescence shows great potential for anti-counterfeiting technology and imaging by taking advantage of a background-free signal. Current anti-counterfeiting technologies face the challenge of low security and the inconvenience of being limited to visible light emission, as emitters in the NIR optical windows are required for such applications. Here, we report the preparation of a series of Zn_1+xGa_2−2xSn_xO₄ nanoparticles (ZGSO NPs) with persistent luminescence in the first and second near-infrared window to overcome these challenges. ZGSO NPs, doped with transition-metal (Cr³⁺ and/or Ni²⁺) and in some cases co-doped with rare-earth (Er³⁺) ions, were successfully prepared using an improved solid-state method with a subsequent milling process to reach sub-200 nm size particles. X-ray diffraction and absorption spectroscopy were used for the analysis of the structure and local crystal field around the dopant ions at different Sn⁴⁺/Ga³⁺ ratios. The size of the NPs was ~150 nm, measured by DLS. Doped ZGSO NPs exhibited intense photoluminescence in the range from red, NIR-I to NIR-II, and even NIR-III, under UV radiation, and showed persistent luminescence at 700 nm (NIR-I) and 1300 nm (NIR-II) after excitation removal. Hence, these NPs were evaluated for multi-level anti-counterfeiting technology.