Understanding the relationship between the electronic state of active sites and N 2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well-defined FeN 4 and MoN 4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN 4 on NRR behavior. The neighboring MoN 4 can regulate the spin state of Fe center in FeN 4 from high-spin (d xy 2 d yz 1 d xz 1 d z 2 1 d x 2 −y 2 1 ) to medium-spin (d xy 2 d yz 2 d xz 1 d z 2 1 ), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN 4 instead of MoN 4 , and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N 2 . As a result, FeMoPPc with medium-spin FeN 4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH 3 yields for NRR than FePPc with high-spin FeN 4 and MoPPc with MoN 4 , respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.

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A flexible mechanoluminophore device that is capable of converting mechanical energy into visualizable patterns through light-emission holds great promise in many applications, such as human-machine interfaces, Internet of Things, wearables, etc. However, the development has been very nascent, and more importantly, existing mechanoluminophore materials or devices emit light that cannot be discernible under ambient light, in particular with slight applied force or deformation. Here we report the development of a low-cost flexible organic mechanoluminophore device, which is constructed based on the multi-layered integration of a high-efficiency, high-contrast top-emitting organic light-emitting device and a piezoelectric generator on a thin polymer substrate. The device is rationalized based on a high-performance top-emitting organic light-emitting device design and maximized piezoelectric generator output through a bending stress optimization and have demonstrated that it is discernible under an ambient illumination as high as 3000 lux. A flexible multifunctional anti-counterfeiting device is further developed by integrating patterned electro-responsive and photo-responsive organic emitters onto the flexible organic mechanoluminophore device, capable of converting mechanical, electrical, and/or optical inputs into light emission and patterned displays.

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