A Pair of Giant Mo Blue Wheels: {Mo ₈₀ } Monomer and {Mo ₁₆₀ } Dimer for Efficient Conversion From Light‐Dominated All‐Weather Environmental Energy to Electricity

Abstract Molybdenum blue (MB) clusters show promise for light‐dominated low‐value energy harvesting due to their broad‐spectrum absorption, tunable redox activity, and chemical stability. However, it is not available to date. Herein, a new type of MB wheels Mo ₁₆₀ dimer and the precise synthesis of its monomer analogs Mo ₈₀ is reported through an amino acid‐mediated assembly strategy. The half‐closed octameric frameworks featuring compressed wheels are orderly constructed by two {Mo _9/10 } and six classical {Mo ₉ } building blocks as well as central {Mo ₃ } or {Mo ₈ } caps. Such structural analogs enable multifunctional light‐dominated energy conversion molecular‐based devices. Mo ₁₆₀ /ethyl cellulose film delivers 430.8 µA photocurrent and 147.7 µV photovoltage under AM 1.5G light. When powered by simulated all‐weather environment combining light, wind, and rain energy, Mo ₁₆₀ film achieves an ideal output power density of ≈0.11 mW m ⁻² at low impedance (≈10 Ω) with long‐term durability, which is 2.58 times higher than that of Mo ₈₀ film and even tens of times better than other types of polyoxometalate film. Theoretical investigations focusing on the electronic characteristics of key building blocks in MB clusters have elucidated molecular‐level structure‐property relationships. This work advances the controlled synthesis of giant polyoxometalates and their implementation in light‐dominated low‐value energy conversion technologies.