New Approach toward Dual-Emissive Organic–Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals

Inorganic–organic
hybrid luminescent materials have received
great attention for their potential applications in a wide range of
clean/renewable energy-related areas, including photovoltaics and
solid-state lighting. Herein, we present a unique and general “Mn
+ Cu” approach by blending two earth-abundant luminogenic metals,
manganese and copper, within a single ionic structure to construct
a remarkable family of low-cost and multifunctional hybrid materials
featuring dual emission, as well as triboluminescence and second-harmonic
generation response. The novel hybrid materials are made of diphosphine
dioxide-chelated [Mn­(O∧O)3]2+ cations
and various anionic [CuxIy](y−x)– clusters, ensuring manifestation of dual phosphorescence
streamed from octahedral Mn2+ ions (605–648 nm)
and iodocuprate anions (480–728 nm). Noteworthily, the relative
ratio of the emission bands, and hence a resulting emission chromaticity,
can be tuned in a wide range through modification of cluster [CuxIy](y−x)– modules. The
structural diversity, enhanced robustness, and up to 100% luminescence
quantum yield make the designed materials promising phosphors for
lighting and sensing applications.

无机-有机杂化发光材料因其在光伏、固态照明等诸多清洁/可再生能源相关领域的应用潜力而受到广泛关注。本文中，我们提出了一种独特且普适的“Mn + Cu”策略：将锰、铜两种储量丰富的发光金属引入单一离子结构中，以此构建出一系列兼具双发射、摩擦发光与二次谐波产生响应的低成本多功能杂化材料体系。该新型杂化材料由二膦二氧化物螯合的[Mn(O∧O)₃]²⁺阳离子与多种阴离子型[CuxIy](y−x)⁻团簇构成，可呈现出源自八面体Mn²⁺离子（605~648 nm）与碘铜酸根阴离子（480~728 nm）的双磷光发射。值得注意的是，通过修饰[CuxIy](y−x)⁻团簇模块，可在宽范围内调节发射带的相对强度比，进而实现发射色度的精准调控。该类材料兼具结构多样性、优异的稳定性与高达100%的发光量子产率，使其成为照明与传感领域极具应用潜力的荧光材料。